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ELECTRONIC STRUCTURE OF ATOMS/                      RELATIONSHIP BETWEEN ATOMS AND
  QUANTUM THEORY (CHAPTER 7)                                     ENERGY

       What have we learned ?                           Atoms + energy            emit light

 1) Atoms are the building blocks of matter.       A GOOD EXAMPLE IS:
 2) Atoms are composed of a dense nucleus
  )     m        mp       f
   (protons and neutrons) with electrons far         Different elements (atoms) emit
   removed from the nucleus.                         light of different colors (red, green,
 3) Stoichiometry.                                   yellow, orange, blue).
 4) Elements are arranged in a periodic table.
 5) Behavior of gases (laws and theory).
 6) Basics of thermochemistry.




        What we don't know ?                                  M*             M + light
                                                           excited            emission
                                                            atom
 1) Why atoms combine to form molecules ?
 2) Why the periodic table has its particular
 arrangement of the elements ?
                                                            M + light            M*
 3) What is the detailed structure of an atom               absorption          excited
 (electrons) ?                                                                   atom
 4) Why atoms combine to form compounds
 with particular formulas ?                      Light interacts with atoms in specific ways –
 5) Why elements (main group, Group A) form      gain information on the electronic structure of
 stable monatomic ions with a particular         atoms by studying this interaction.
 charge (e.g., Na+, Ca2+, O2-, Cl-) ?




         MOLECULAR FORMULAS

• Atoms combine to form molecules with
  specific formulas.                             Light is electromagnetic radiation and is a
• How atoms combine depends on the               wave and it has wavelike characteristics.
  distribution or arrangement of electrons
  around the nucleus of the atom (i.e.,
  electronic structure).
   l      i           )                          Wave: Vibrating disturbance by which energy
• Early experimental evidence aided in           is transmitted.
  developing an understanding of atomic
  structure:                                     Water waves, sound waves, etc.
  – J. J. Thomson’s discovery of the electron.         Waves are characterized by: frequency
  – Rutherford’s Nuclear Model of the Atom.                                        wavelength
                                                                                   amplitude




                                                                                                   1
Figure 7.2




                                                          Frequency/Amplitude(intensity) of
                                                                   Various Waves




                                      Figure 7.2




        WAVE CHARACTERISTICS                        Speed of wave propagation =  X 
                                                                 1             distance
Wavelength (  lambda): The distance              distance  
                                                                    speed                    speed
(length) between adjacent peaks on the wave.                  time              time
SI unit: meter (m).                                Electromagnetic radiation (radiant energy, light).

   q    y
Frequency (  nu): The number of waves            Speed of light (c) = 3.00 X 108 m/s (in a vacuum)
                                                    p         g                         (          )
(wavelengths) that pass a point per second.              (186,000 miles/s or 671,000,000 mph)
The SI unit of frequency is the hertz (Hz).        This radiation does not need a medium for
SI units: 1/s or s-1 or hertz (Hz).                propagation - can travel through a vacuum.
                                                                 c =    = constant
Amplitude (intensity): The vertical distance
from the mid-line to the peak (intensity).         If  increases, then  decreases (inverse
                                                   relationship).




                                                                                                        2
Example: Frequency and Wavelength

 What is the frequency () of radiation that
 has a wavelength () of 1.5 X 10-2 m ?

        Start this problem with   c =  
 Rearrange the equation and solve for :
 R          h       i     d l f


        c 3.00 X 10 8 m/s
                        2 X 1010 s -1
         1.5 X 10 - 2 m
                           or 2 X 1010 Hz
                                                                   Figure 7.4




          Electromagnetic Radiation
                                                   Max Planck (1900)
Maxwell (1873): Developed a theory for light.
                                                Studied radiation emitted by
He proposed that light waves consists of two    matter (objects). All objects
components; a vibrating electric field and a    emit electromagnetic radiation.
vibrating magnetic field.

Hence, the term “electromagnetic radiation”.

This radiation involves the transmission of
energy from one place to another.




                                                Postulated that atoms and molecules can emit or
                                                absorb energy (radiation) only in discrete
                                                quantities.
                     Figure 7.3                 Energy in matter is quantized, not continuous !!




                                                                                                   3
QUANTIZED ENERGY
                                                               PHOTOELECTRIC
What is a quantum of energy ?                                     EFFECT
  – The smallest increment of energy that can be    These observations of the
    emitted or absorbed in the form of              photoelectric effect could not be
    electromagnetic energy (light) by matter.
                                                    explained by the wave theory of light.
Energy (E) of a single quantum is given by:
                 E = h                             Albert Ei t i (1905) Considered that li ht i
                                                    Alb t Einstein (1905): C  id   d th t light is
     E = energy (J)                                 composed of a stream of particles that are
      = frequency (1/s)                            called photons (or quanta-packets of
     h = Planck's constant (6.63 X 10-34 J · s)     energy).
  – Units: E = (J · s)(1/s) = J (energy)
                                                    Extended Planck’s idea’s.




PHOTOELECTRIC EFFECT: Light can cause                            Photoelectric Effect
electrons to be ejected from a metal surface.
         light
                                elec t r o n




                  met al   surf ace
There is a threshold frequency () for electron
ejection and if light has a  less than the
threshold, no electrons are ejected.
At a  greater than the threshold, the number
of electrons ejected is proportional to the light
intensity.                                                             Figure 7.5




                                                                                                     4
Each photon of light has an energy, E:
            E = h ·  (Planck’s ideas)
Energy of a photon is directly proportional to
the frequency.

Energy of a p
    gy f photon is important and dictates
                         p
how light interacts with matter.

Electromagnetic radiation (light) has both
wave-like and particle-like properties.

The dual nature of light!!!
                                                                           Figure 7.4




           Problem: Quantized Energy
A typical laser pointer has red light -
                                                        Energy of Electromagnetic Radiation
wavelength 630 nanometers (6.3 X 10-7 meters).
                                                        • Given by E = h = hc/
What is the energy of one photon of light
with  = 630 nm?                                        • Short wavelengths ()  high energy;
                                                          e.g., X rays - very dama in to life
                                                          e     X-rays        damaging

            hc (6.63 X 10 - 34 J s)(3.0 X 10 8 m/s)     • Long wavelengths ()  low energy;
 E  hν                                                 e.g., radio waves - safe
            λ           (6.3 X 10 - 7 m)

                3.16 X 10 -19 J




            Electromagnetic Spectrum                                 ATOMIC SPECTRA
Radio waves                                             Experimental observations of the interaction of
                                   Some Facts           radiation with matter.
Microwave
                               Inverse relationship       Atom + h           Atom*      absorption
Infrared                       between  and 
                                                          Atom*           Atom + h      emission
Visible                         (lambda) ranges
                               from 1013 to 10-3 nm   Atoms absorb and emit light with discrete energy
Ultraviolet                                           (’s and ’s). They can have only particular
                                (nu) ranges from     amounts of energy – energy of atoms is quantized.
                               104 Hertz (Hz) to
X-rays
                               1020 Hz
                                                      Energy levels of atoms - it's the electrons that
Gamma rays                                            are important - energy levels of the electrons.
                          




                                                                                                          5
Atomic Spectrum of Hydrogen Atoms

Simplest element, it has the simplest spectrum.

See a series of lines in the atomic spectrum of
hydrogen atoms.

Only discrete ’s and ’ of li ht are absorbed
O l di     t   ’    d ’s f light      b b d
or emitted by hydrogen atoms.

This resulting spectrum is unique for hydrogen -
different from all other elements.




 Experiment to View the Atomic Spectrum of H
                                                                       Atomic Spectra of Hydrogen

                                                              Numerous lines ranging from the ultraviolet ( <
                                                              400 nm) to the infrared region ( > 800 nm).

                                                 Figure 7.6   J. J. Balmer (1885): Studied the lines in the
                                                              visible portion of the the spectrum (400 nm to
                                                              700 nm).




        energy       energy        emission
   H2            H            H*              H + light




                 Continuous Spectrum




                                                              Found a simple equation (
                                                              F   d    i l       ti (empirical) for calculating
                                                                                           i i l) f     l l ti
                                                              the emission wavelengths in the visible region:


                                                                 1       1   1 
                  Figure 7.6                                        RH  2  2       RH = Rydberg constant
                                                                 λ      2   n           = 109,678 cm-1
  Each type of atom (element) has its own
  unique spectrum (lines).                                      n = 3, 4, 5, and 6




                                                                                                                  6
Atomic Spectra of Hydrogen

 General equation for calculating all emission                                            Will the
 lines in the hydrogen spectrum:                                                         photon be
                                                                                        absorbed ?
   1       1   1        RH = Rydberg constant
      RH  2  2           = 109,678 cm-1
                                  ,
   λ      n      
           i nf 
  Restriction: ni and nf are whole numbers
                                                        1st Bohr orbit

                                                                                    If of the proper
  ranging from 1 to infinity.                           2nd Bohr orbit             energy, the photon
                                                                                  is absorbed and the
  The above equation is called the Rydberg              3rd Bohr orbit            electron jumps to a
  equation.                                                                       higher energy orbit.




   Different Series of Spectral Lines
              for H atoms
                                                                                        Absorption




                                                         1st Bohr orbit



Lyman series: nf = 1;     ni = 2, 3, 4,…(ultraviolet)
                                                          2nd Bohr orbit
                                                                                 Electron can return to
Balmer series: nf = 2;    ni = 3, 4, 5,…(visible)         3rd Bohr orbit          the ground state by
Paschen series: nf = 3;   ni = 4, 5, 6, …(infrared)                               emitting a photon of
Brackett series:nf = 4;   ni = 5, 6, 7, …(infrared)                                 the same energy.




   EXPLANATION OF H-LINE SPECTRUM

Niels Bohr (1913), Danish physicist
Developed a theoretical model for the                                                      Emission
hydrogen atom.

Bohr viewed the electron as moving around the
nucleus in only fixed (discrete) radii or orbits
(planets in a solar system).                                   1st Bohr orbit



This placed restrictions on the sizes of the orbits
                                                               2nd Bohr orbit


and the energy that the electron can have in a                  3rd Bohr orbit
given orbit (departure from classical physics).




                                                                                                          7
Potential
                                                                   Energy




                           Figure 7.9




Bohr described the potential energy of the                            Bohr’s Model of H-atom
electron in the hydrogen atom by a simple (?)
                                                           n = 1: First Bohr orbit, ground state, lowest
equation:
                                                           potential energy.
                        2    4
                           2π me
                 E                                       If the hydrogen atom in the ground state
                             n2 h2                         absorbs energy, then the electron goes to a
 m = mass of the electron (9 109 X 10-31 kg)
                           (9.109                          higher energy (larger) orbit (n = 2, 3, 4, ...);
                                                             g         gy ( g )         (                )
 e = charge of the electron (1.602 X 10-19 C,              called excited states.
                 (1.519 X 10-14 kg1/2 m3/2 s-1)            For transitions in the Bohr Model of the H-atom
 h = Planck’s constant (6.63 X 10-34 J · s)
 n = quantum number (1, 2, 3, ….)                          n = 1 to n = 2 absorbs energy
                 2
               2π me   4                                                                            same energy
       R'H                  2.18 X 10-18 J                n = 2 to n = 1 emits energy
                 h2




                                                                      Bohr’s Hydrogen Atom
           Bohr’s Equation of Energy
               R' 
       E n  - 2H        n  1, 2, 3, ...  (integers)
               n 
       R’H: constant (2.18 X 10-18 J)
       n:   quantum number
            (has values from 1 to  )

  Negative sign: Potential energy of the atom <
  potential energy of H+ and a free electron.                    b  R’H

          Lowest energy, n = 1 (E < 0)
          Highest energy, n =  (E = 0)                                 R' 
                                                                E n  - 2H    n  1, 2, 3, ...  (integers)
                                                                        n 




                                                                                                                  8
Example: What is the change in energy of the
                                                hydrogen atom when the electron goes from the
                                                n = 3 to the n = 1 level ?
                                                Use the equation for the change in energy for H-
                                                atom:

                                                                1   1    
                                                     ΔE  R' H  2  2
                                                          R               
                                                               n n       
                                                                i    f   
                                                                           1 1
                                                     ΔE  2.18 X 10 -18 J  2  2   1.94 X 10-18 J
                                                                          3 1 

                                                 A photon of light energy is emitted, since ni
                                                 > nf , E is negative.
                     Figure 7.9




   Energy of Transitions in Bohr H-Atom          What is the frequency () and wavelength ()
                                                 of this photon ?
                                                  Use Einstein‘s equation and solve for :
   Energy of the                R' H                   ΔE  hν
   Initial State:       E i   2
                                n      
                                        
                                i                        ΔE    1.94 X 10 -18 J
                                                      ν                             2.93 X 1015 Hz
                                                            h   6 63 X 10 - 34 J  s
                                                                6.63

                                R'                 Calculate wavelength () :
   Energy of Final
                        E f   2H 
   State:                       n                 c  λν
                                f 
                                                         c 3.00 X 10 8 m/s
                                                    λ                     1.02 X 10 - 7 m  102 nm
                                                         ν 2.93 X 1015 /s




   Energy of Transitions in Bohr H-Atom

                         - R'   - R' 
       ΔE  E f  E i   2 H    2 H 
                         n   n 
                         f   i 
                  1   1 
       ΔE  R' H  2  2   hν
            R
                 n n 
                  i    f 



If ni > nf , then a photon is emitted, E is
negative.
If ni < nf , then a photon is absorbed, E is
positive.




                                                                                                        9
Relationship between Bohr’s equation and the               de Broglie’s Hypothesis (1924)
Rydberg equation:                                  • If electromagnetic radiation (light) can have
                                                     particle-like properties (photon), then electrons
Bohr’s equation:                                     may also possess wave-like properties.
                                                   • Electrons do indeed have both particle and
                                1   1 
                     ΔE  R' H  2  2              wave-like properties !!! Electrons are similar to
                               n n                   g
                                                     light.
                                i    f 
                                                   • From Einstein's theory of relativity:
Rydberg Equation:
                                                                   E  mc 2
                 1       1   1                                   m  mass
                    RH  2  2                                   c  speed of light
                 λ      n      
                         i nf                      This equation relates energy and mass.




Rydberg constant calculated from Bohr’s theory:               de Broglie’s Hypothesis
             ΔE  hv 
                       hc      1
                           hc                          Using photon equation for light:
                       λ       λ
                                                                       hc             c  
                                                            E  h 
                    R' H in J                                                           c
         
    RH in cm 1       hc
                                                                                      
                                                                                           
                                                       Substitute mc2 for E and solve for :
                            1
               2.18 X 10-18 J        1m 
                                           
                                    
      6.63 X 10 J  s 3.00 X 10 m/s  100 cm 
               - 34              8
                                                                                 hc
                                                                        mc 2 
    109,600 cm -1                                                               
                                                                         and
Agrees well with the known Rydberg constant                                h
value (109,678 cm-1).                                                   
                                                                           mc




                       Bohr’s Theory
                                                              de Broglie’s Hypothesis
• Only works for the hydrogen atom; not a
  general theory, it is limited and incomplete.    • Notice that the product, mc, is defined as
                                                     momentum (i.e., mass X velocity).
• Used some elements of "classical physics",
  which do not apply to atomic and subatomic       • This equation then relates wavelength,
  particles !!!!                                     mass, and velocity.

• Questions for Bohr:                              • For an electron, its speed must be less than
  – Why is energy of the electron quantized?         the speed of light, c. We can simply
  – Why are electrons restricted to only certain     substitute in for the speed (velocity) of the
    orbits?                                          electron, v.
  – Why are atoms stable (exist)?




                                                                                                         10
The wavelength of an electron (a particle) is
 given by:                                                                  de Broglie Wavelength For a Baseball
                                                                                                     h
           
                h                                                                              
               mv                                                                                    mv
           v  velocity (m/s)
                                                                          For the baseball:
           m v  momentum (particle property)
                          (p        p p y)
           Units :                                                           mass is 0.14 kg and velocity is 40 m/s

           kg  m
                    2
                                                                                      6.63 x 10 -34 J  s
               s  m (distance, wavelength)                                                              1.2 x 10 -34 m
        kg  m
                                                                                     (0.14 kg)(40 m/s)
               s
Electrons, protons, and neutrons experience                              Wave properties of particles only apply to atomic
diffraction - wave property !!!!                                         and subatomic particles – not to baseballs !!!!




     Diffraction Pattern for Al with X-rays and
                      Electrons
                                                                         QUANTUM MECHANICS (WAVE MECHANCIS)


                                                                           Erwin Schrödinger (1926)
                                                                           Nobel Prize (1933)

                                                                         Applies wave properties of matter to explain
                                                                          pp          p p                       p
                                                                         atomic properties.

                                                                         Bohr’s theory: Electrons move around the nucleus
                                                                         in fixed (discrete) orbits (e.g., solar system).

                electrons          X-rays                                Wave mechanics: Treats electrons as waves –
                        Figure 7.14                                      difficult to perceive.




 Example:                                                                 This theory leads to a series of mathematical
 Calculate the de Broglie wavelength for an                               functions called wave functions.
 electron travelling at 1 % the speed of light
 (3.00 X 106 m/s).                                                        The electron wave function is called an orbital
                                    h                                     (atomic orbital).
Use de Broglie’s relationship:   m v

For an electron,                                                          The t
                                                                          Th term “orbital” i used to distinguish f
                                                                                    “ bit l” is    d t di ti  i h from
                                                                          Bohr’s ideas of fixed orbits.
        m = 9.11 X 10-31 kg; v = 3.00 X 106 m/s

             6.63 X 10 - 34 J  s
λ                                          2.43 X 10 -10 m or 243 pm
     9.11 X 10- 31 kg3.00 X 106 m/s 
      Follow the units through!!!!




                                                                                                                             11
Interference of Waves                                        Electron Waves


                       Two waves with the same
                       frequency add together if
                       they are “in phase” (their
                       peaks exactly match).

                       Constructive interference.         4 wavelengths                    3.6 wavelengths



                                                                                                     destructive
                                                                                                     interference




             Interference of Waves
                                                     These electron wave functions are quantized.
                                                     They must have integral numbers of
                       Two waves with the same       wavelengths, otherwise destructive interference
                       frequency but exactly         will result in annihilation of the electron wave.
                       “out of phase” (peak of
                       one wave matches a valley
                       of the other wave) cancel
                        f h     h       )      l
                       out (destroyed).              Energy changes in an atom - simply changes in
                                                     wave functions (patterns) which are quantized.
                       Destructive interference.
                                                     Electrons exist only in those regions in which
                                                     their waves reinforce each other.




                                                    In wave mechanics, the electrons do not orbit the
 Allowed (Stable) Orbital:                          nucleus in fixed, circular orbits (Bohr’s ideas).

     4 wavelengths –                                Rather, the electron wave function takes on a
constructive interference                           particular shape, a probability of finding the
                                                    electron in a particular volume of space.

                                                    An atomic orbital is characterized by:
   Forbidden (Unstable)
         Orbital
                                                                             energy
   4.5 wavelengths –                                                         size
destructive interference                                                     shape
                                                                             orientation in space




                                                                                                                    12
The “p” Orbitals: Are not spherical, consist of
TYPES (SHAPES) OF ATOMIC ORBITALS
                                             two lobes of electron density about the nucleus.
 The “s” Orbitals: Have a spherical shape:




 The “s” Orbitals: Have a spherical shape:
                                             There are three individual “p” orbitals, differ
                                             only in their orientation in space:




                            Figure 7.18                         Figure 7.20




                                             The three individual “p” orbitals, represented
 The “s” Orbitals: Have a spherical shape:   in an atom:




                                                                                                13
The “d” Orbitals: Have a more complex shape (four                    QUANTUM NUMBERS
lobes of electron density about the nucleus).
Five individual “d” orbitals, differ only in their     • PRINCIPAL QUANTUM NUMBER (n) Determines
orientation in space:                                    the energy and size of an orbital.
                                                          – Allowed values  1, 2, 3,…  (positive
                                                            integers)
                                                       • As n increases the energy and size of the
                                                               increases,
                                         Figure 7.21     orbital increases.
                                                       • All orbitals that have the same value for "n" are
                                                         in the same "shell".
                                                                   n = 1 shell    (first shell)
                                                                   n = 2 shell    (second shell)
                                                                   n = 3 shell    (third shell)
                                                                                        etc.




The “f” Orbitals: Have a very complex shape (eight
                                                       Angular Momentum (Shape) Quantum Number (l):
lobes of electron density about the nucleus).
                                                         This quantum number determines the shape of
There are seven individual “f” orbitals that vary
                                                         the orbital.
only in their orientation in space.
                                                       Divides a shell into smaller groups called subshells.
                                                       Only certain "l" values are possible-limited by "n":
                                                       Can have integral values from zero to n – 1
                                                                      (0, 1, 2, 3,
                                                                      (0 1 2 3 ....n - 1)


                                                                       Shells           Subshells
                                                                       n=1              l=0
                                                                       n=2            l = 0, 1
                                                                       n=3          l = 0, 1, 2




                                                        Angular Momentum (Shape) Quantum Number (l)
                                                        Typically, a letter code is used to specify the
               Quantum Numbers                          “l” values:

                                                                 l     0        1   2      3      4   5….
  Bohr’s theory used a single quantum number (n)
  to describe an orbit.                                       letter    s       p   d      f      g   h….

  Quantum mechanics theory (wave mechanics)            Letter designations  Nature of spectral
  has three quantum numbers (n, l, ml) to describe     feature:
  an atomic orbital.                                                s  Sharp-very narrow
                                                                    p  Principle-very strong
                                                                    d  Diffuse-spread out
                                                                    f  Fundamental




                                                                                                               14
Angular Momentum (Shape) Quantum Number (l)                MAGNETIC QUANTUM NUMBER (ml):

  To designate a subshell, we need to specify          • For a "d" subshell:
  both "n" (number) and "l" (letter):                    l = 2   then     ml = -2, -1, 0, 1, 2
                                                                       (five ml values)
            Shell      Subshell    designation
            n=1           l=0            1s              There are five orbitals i a "d" subshell.
                                                       • Th               bit l in         b h ll
            n=2           l=0            2s
            n=2           l=1            2p              • For the "f" subshell:
                                                               l = 3 then ml = -3, -2, -1, 0, 1, 2, 3
            n=3           l=2            3d
                                                                            (seven ml values)

                                                         • There are seven orbitals in a "f" subshell.




 Angular Momentum (Shape) Quantum Number (l)


 • For a given "n" value, there are small
   differences in energy for various "l"
   values.

 • Order of increasing energy of subshells in
   the same shell:
               s < p < d < f < g….
                    increasing energy
                     4s < 4p < 4d < 4f




      MAGNETIC QUANTUM NUMBER (ml)                            REPRESENTATION OF ORBITALS
• Describes the orientation in space relative to                     (shapes and sizes)
  other orbitals of that same subshell (l).
   – Divides a subshell into individual orbitals.       Electron wave form (function) considers a
• Possible ml values :(-l, -l + 1, ....+l)              probability of finding the electron around the
• For the "s" subshell:                                 nucleus.
           l = 0    then    ml = 0
• There is only a single orbital in an “s” subshell.    Define the size and shape of an orbital by a
• For the "p" subshell:                                 90% probability diagram (90% of the electron
                                                        density lies within these boundaries, 90 %
           l = 1    then    ml = -1, 0, 1
                 (three ml values)                      chance that the electron will be found within
                                                        this volume).
• There are three orbitals in a "p" subshell.




                                                                                                         15
The “s” Orbitals:
      n = 1 to infinity; l = 0;          ml = 0
                                                  There are three individual “p” orbitals in a “p”
Have a spherical shape:
                                                  subshell, differ only in their orientation in
                                                  space:




                                                                 The “d” Orbitals:

                                                     n  3;     l = 2;    ml = -2, -1, 0, 1, 2

                                                  Five individual orbitals in a “d” subshell.

                                                  They have a more complex shape, differ
                                                  only in their orientation in space.

                                                  Each have the same energy, size, and
               1s   <     2s    <   3s
                                                  shape.
            Increasing size and energy




              The “p” Orbitals:                   Five individual “d” orbitals, differ only in their
                                                  orientation in space:
     n  2;      l = 1;        ml = -1, 0, 1

Three individual orbitals in a “p” subshell.

They all have the same shape, size, and
energy - differ only in their orientation in
space.

Consist of two lobes of electron density about
the nucleus.


                                                                         Figure 7.21




                                                                                                       16
THE “f” ORBITALS:
                                                    MAGNETIC PROPERTIES OF THE ELECTRON
n  4 ; l = 3; ml = -3,-2, -1, 0, 1, 2, 3

Seven individual orbitals in the “f” subshell.
Very complex shape (8 lobes of electron density)
and differ only in their orientation in space.

Each have the same energy, size and
shape.

Orbitals with the same energy, i.e., the
three p orbs, five d orbs, etc. are said to
be degenerate.




                                                                   ELECTRON SPIN
 MAGNETIC PROPERTIES OF THE ELECTRON
                                                     The quantized spin of the electron is
It was found that atoms of some elements have        verified by experiment.
magnetic fields.

This was explained by considering that the
electron is spinning.


From electromagnetic theory, a spinning charge
generates a magnetic field.


Hence, electrons behave like very small magnets.        Figure 7.17




              ELECTRON SPIN

Quantum mechanics theory predicts that the         A complete set of quantum numbers to
electron has only two possible spin states.        describe an electron’s wave form (function):

Hence, electron spin is quantized.

An l
A electron spin quantum number ( s) i
              i             b (m is
assigned to the electron.                                      n      l   ml   ms
        ms has values of +1/2 and -1/2

These two spin states generate magnetic fields
that are directly opposed.




                                                                                                  17
Pauli exclusion principle: States that no two
electrons in an atom can have the same set of
four quantum numbers.                                                    Electrons in Shells
      n, l, ml  specify an orbital                                                        maximum # of
                                                                  Shell (n)   Subshells      electrons
                                                                     1           s              2
       ms  specify electron spin                                    2          s, p            8
                                                                     3         s, p, d          18
Consequently, no more than two electrons can
                                                                     4        s, p, d, f        32
be in an orbital. If an orbital contains two
electrons, then they must have opposite spin
quantum numbers (ms values).




               Quantum Numbers                                    Quantum (Wave) Mechanics
                                                         Quantum Numbers:
      n          l      designation           ml
                         (subshell)
                                                           Principal - n (energy & size of orbitals)
     value     value                        values         Angular Momentum - l (shape of orbitals)
       1         0            1s              0            Magnetic - ml (orientation of orbitals)
      2          0            2s               0           Spin - ms (spin of e-’s in orbitals)
                                                         Pauli Exclusion P i i l
                                                         P li E l i Principle:
      2          1            2p            -1, 0, 1
                                                            – No two electrons in an atom can have
      3          0            3s               0             the same set of four quantum numbers
      3          1            3p            -1, 0, 1
                                                           – n, l, ml  specify an orbital
      3          2            3d       -2, -1, 0, 1, 2     – e- spin distinguishes the two e-’s in an
                                                             orbital (ms)




                                                         Electron Configuration (Electronic Structure)
             Electrons in Subshells
                                                          The distribution of electrons among orbitals of
                         # of      maximum #              an atom.
          Subshell     orbitals    of electrons
             s            1             2                 Ground State electron configuration: Lowest
             p            3             6                 energy arrangement of electrons.
             d            5            10
                                                          Electron configuration: List subshells that
             f            7            14
                                                          contain electrons and designate their
                                                          populations by appropriate superscripts.




                                                                                                            18
Hydrogen Atom Electron Configuration                    Ground State electron configuration of O:
                                                                           1s2 2s2 2p4
                              # of electrons in
                                the subshell           • Orbital Diagram: Shows each orbital by a box
                                                         (circle) and how the electrons are placed in
                                                         the orbitals with their spins specified.
      H         1e-     1s1
                                                       • s subshells fill with electron pairs; one spin up
                              Angular Momentum           and one spin down in the 1s; same for the 2s
                                                            d          d          h           f    h
           principal          (shape) quantum #        • This leaves 4 electrons for the 2p subshell.
          quantum #               (subshell)
            (shell)
                                                                                      Why did we fill the
This electronic structure accounts for the                                            2p subshell this way?
observed chemical properties of the                      1s2   2s2        2p4
hydrogen atom.




     Electron Configuration For Helium                 Many different ways to distribute the four
                                                       electrons in the 3 individual p orbitals in the p
  Helium is in Group 8A, Period 1 of the Periodic      subshell.
  Table (Atomic Number 2)
                               # of electrons in       Hund's rule: For a partially filled subshell,
                                 the subshell          the lowest energy arrangement will have the
                                                       maximum number of unpaired electrons (orbitals
                                                                           f p                 (
       He        2e-    1s2                            with only a single electron) each with the same
                                   Angular Momentum    (parallel) spin state.
             principal             (shape) quantum #
            quantum #                  (subshell)

He: the first Noble Gas; inert, unreactive; Why ?
                                                                                2p4
Because the n = 1 shell is filled with 2 electrons




                                                       Orbital diagrams for a p subshell with 4 electrons
    Oxygen, Group 6A, Period 2; Element 8
                                                        It doesn’t matter how these three individual p
                                                        orbitals are displayed, one orbital must have
   Has 8 e-’s, the n = 1 shell is filled with 2         two electrons with paired spins and two orbitals
   electrons, the other 6 electrons go into the         must each contain one electron with parallel
   n = 2 shell.                                         spin.


            O          8e-        1 s2 2 s2 2 p 4                                     These are all
                                                                                      equivalent orbital
                                                                                      diagrams for a p4
                                                                                      subshell.




                                                                                                              19
Orbital diagrams for a p subshell with 4 electrons
                                                                          MAGNETIC PROPERTIES OF ATOMS
    Higher energy arrangements of electrons                      Predict magnetic properties (diamagnetic or
                                                                 paramagnetic) from ground state electron
                                                                 configurations and orbital diagrams.

                                                                        Consider Nitrogen with 7 electrons:

                                                                 N
                                                                 7e-

                                                                              1s2          2s2              2p3
     These are higher energy orbital
     diagrams for a p4 subshell.
                                                                  It is paramagnetic with 3 unpaired electrons.




   MAGNETIC PROPERTIES OF ATOMS                                               MAGNETIC PROPERTIES OF ATOMS
 If all electrons in an atom are paired in orbitals
 (i.e., orbitals are filled), then the magnetic
                                                                 C
 moments (fields) of the electrons exactly cancel.
                                                                 6e-
 The atom will not be affected (attracted) by a
 magnet. The atom is said to be diamagnetic.                               1s2    2s2             2p2
                                                                          p
                                                                          paramagnetic with 2 unpaired electrons
                                                                                g               p

                                             diamagnetic
                                                                Al
                                                                13 e-
                                    1s2
                                                                         1s2        2s2           2p6       3s2        3p1
                                e.g.,     Helium (He -   2e-)             paramagnetic with 1 unpaired electron




         MAGNETIC PROPERTIES OF ATOMS                                    MAGNETIC PROPERTIES OF ATOMS
 If an atom has a subshell that is partially
 filled, then the magnetic moments of "unpaired"                                                        It has no unpaired
                                                                        Be
 electrons will add together to make the atom                                                           electrons, so it is
                                                                        4e-
 magnetic. The atom will be attracted by a                                                              diamagnetic.
 magnet. It is said to be paramagnetic.                                              1s2         2s2


                H                   paramagnetic                Ne
                                                                10e-
                          1s1
                                                                              1s2          2s2              2p6
Oxygen                                    Paramagnetic, 2
                                          unpaired e-’s                 diamagnetic with no unpaired electrons
          1s2       2s2     2p4




                                                                                                                              20
Ground-state electron configurations for
               atoms with many electrons:


               Fill orbitals by energy, lowest energy orbitals
               (subshells) are filled according to:



               1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p

                “Aufbau principle”: German for “building up”;
                put electrons into the lowest energy orbitals.




              A simple way to
              remember this order:
              Set
              S t up th s subshells
                      the     b h ll
              in a column, then the p
              subshells in a column
              next to it, then the d
              subshells in a column
              next to it, etc.

Figure 7.23




              Then fill along the diagonals of the column




                                                            Figure 7.24




              1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p




                                                                          21
An Example for a Many Electron Atom                Filled shells yield particularly stable electron
Consider Iron, Atomic Number 26 (# of protons)       configurations, e.g., the noble gases:
                                                       He 2e- 1s2
                    26Fe    26 e-
                                                       Ne 10e- 1s2 2s2 2p6
Electron Configuration: Fill the subshells             Ar 18e- 1s2 2s2 2p6 3s2 3p6
according to their energy:                             K 36e- 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6
                                                       Kr
                                                     We will be concerned with the outer-shell
              1s2 2s2 2p6 3s2 3p6 4s2 3d6            electrons. These are called valence electrons and
                                                     they control the chemical properties of the atom.

                                                     The electrons in the inner-shells are called the
                                                     core electrons. The have little effect on chemical
                                                     properties.




What are the magnetic properties for this              ABBREVIATED ELECTRON CONFIGURATIONS
electron configuration of Fe??

Focus on the 3d subshell (five orbitals, partially   The noble gas core will be indicated by the
filled subshell).                                    appropriate noble gas element symbol in brackets
                                                     followed by the additional electrons:

                                                     Fe   1s2 2s2 2p6 3s2 3p6 4s2 3d6  [Ar] 4s2 3d6

                       3d6                           For the halogens in Group 7A:
                                                              F      [He] 2s2 2p5
Fe - Paramagnetic with four unpaired electrons.
                                                              Cl     [Ne] 3s2 3p5
                                                              Br     [Ar] 4s2 3d10 4p5




 Electron configurations of the elements are          Use the periodic table to determine the last
 listed in Table 7.3 (page 300).                      subshell that is being filled:

Some exceptions to our guidelines-we will ignore       Groups 1A and 2A            s subshells
these exceptions.
                                                       Groups 3A to 8A             p subshells
For example: Chromium (Cr-24 e-)
F          mp             m um (
1s 2 2s2 2p6 3s2 3p6 4s2 3d4     expected              Transition metals           d subshells
1s2 2s2 2p6 3s2 3p6 4s1 3d5      actual
                                                       Lanthanides                 f subshells
For example: Copper (Cu-29 e-)
                                                       Actinides                   f subshells
1s2 2s2 2p6 3s2 3p6 4s2 3d9  expected
1s2 2s2 2p6 3s2 3p6 4s1 3d10 actual




                                                                                                          22
Figure 7.28




 Why do elements in a group have similar
 chemical properties? Because they have
 similar valence shell (outer shell) electron
 configurations.
                        Group 2A - Alkaline earths
Group 7A - Halogens          Be          2s2
      F     2s22p5
                             Mg          3s2

     Cl     3s23p5          Ca           4s2
                            Sr           5s2
     Br     4s24p5
                            Ba           6s2
     I      5s25p5          Ra           7s2
          ns2 np5                  ns2




                                                     23

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Chapter 7

  • 1. ELECTRONIC STRUCTURE OF ATOMS/ RELATIONSHIP BETWEEN ATOMS AND QUANTUM THEORY (CHAPTER 7) ENERGY What have we learned ? Atoms + energy emit light 1) Atoms are the building blocks of matter. A GOOD EXAMPLE IS: 2) Atoms are composed of a dense nucleus ) m mp f (protons and neutrons) with electrons far Different elements (atoms) emit removed from the nucleus. light of different colors (red, green, 3) Stoichiometry. yellow, orange, blue). 4) Elements are arranged in a periodic table. 5) Behavior of gases (laws and theory). 6) Basics of thermochemistry. What we don't know ? M* M + light excited emission atom 1) Why atoms combine to form molecules ? 2) Why the periodic table has its particular arrangement of the elements ? M + light M* 3) What is the detailed structure of an atom absorption excited (electrons) ? atom 4) Why atoms combine to form compounds with particular formulas ? Light interacts with atoms in specific ways – 5) Why elements (main group, Group A) form gain information on the electronic structure of stable monatomic ions with a particular atoms by studying this interaction. charge (e.g., Na+, Ca2+, O2-, Cl-) ? MOLECULAR FORMULAS • Atoms combine to form molecules with specific formulas. Light is electromagnetic radiation and is a • How atoms combine depends on the wave and it has wavelike characteristics. distribution or arrangement of electrons around the nucleus of the atom (i.e., electronic structure). l i ) Wave: Vibrating disturbance by which energy • Early experimental evidence aided in is transmitted. developing an understanding of atomic structure: Water waves, sound waves, etc. – J. J. Thomson’s discovery of the electron. Waves are characterized by: frequency – Rutherford’s Nuclear Model of the Atom. wavelength amplitude 1
  • 2. Figure 7.2 Frequency/Amplitude(intensity) of Various Waves Figure 7.2 WAVE CHARACTERISTICS Speed of wave propagation =  X  1  distance Wavelength (  lambda): The distance distance      speed speed (length) between adjacent peaks on the wave.  time  time SI unit: meter (m). Electromagnetic radiation (radiant energy, light). q y Frequency (  nu): The number of waves Speed of light (c) = 3.00 X 108 m/s (in a vacuum) p g ( ) (wavelengths) that pass a point per second. (186,000 miles/s or 671,000,000 mph) The SI unit of frequency is the hertz (Hz). This radiation does not need a medium for SI units: 1/s or s-1 or hertz (Hz). propagation - can travel through a vacuum. c =    = constant Amplitude (intensity): The vertical distance from the mid-line to the peak (intensity). If  increases, then  decreases (inverse relationship). 2
  • 3. Example: Frequency and Wavelength What is the frequency () of radiation that has a wavelength () of 1.5 X 10-2 m ? Start this problem with c =   Rearrange the equation and solve for : R h i d l f c 3.00 X 10 8 m/s     2 X 1010 s -1  1.5 X 10 - 2 m or 2 X 1010 Hz Figure 7.4 Electromagnetic Radiation Max Planck (1900) Maxwell (1873): Developed a theory for light. Studied radiation emitted by He proposed that light waves consists of two matter (objects). All objects components; a vibrating electric field and a emit electromagnetic radiation. vibrating magnetic field. Hence, the term “electromagnetic radiation”. This radiation involves the transmission of energy from one place to another. Postulated that atoms and molecules can emit or absorb energy (radiation) only in discrete quantities. Figure 7.3 Energy in matter is quantized, not continuous !! 3
  • 4. QUANTIZED ENERGY PHOTOELECTRIC What is a quantum of energy ? EFFECT – The smallest increment of energy that can be These observations of the emitted or absorbed in the form of photoelectric effect could not be electromagnetic energy (light) by matter. explained by the wave theory of light. Energy (E) of a single quantum is given by: E = h Albert Ei t i (1905) Considered that li ht i Alb t Einstein (1905): C id d th t light is E = energy (J) composed of a stream of particles that are  = frequency (1/s) called photons (or quanta-packets of h = Planck's constant (6.63 X 10-34 J · s) energy). – Units: E = (J · s)(1/s) = J (energy) Extended Planck’s idea’s. PHOTOELECTRIC EFFECT: Light can cause Photoelectric Effect electrons to be ejected from a metal surface. light elec t r o n met al surf ace There is a threshold frequency () for electron ejection and if light has a  less than the threshold, no electrons are ejected. At a  greater than the threshold, the number of electrons ejected is proportional to the light intensity. Figure 7.5 4
  • 5. Each photon of light has an energy, E: E = h ·  (Planck’s ideas) Energy of a photon is directly proportional to the frequency. Energy of a p gy f photon is important and dictates p how light interacts with matter. Electromagnetic radiation (light) has both wave-like and particle-like properties. The dual nature of light!!! Figure 7.4 Problem: Quantized Energy A typical laser pointer has red light - Energy of Electromagnetic Radiation wavelength 630 nanometers (6.3 X 10-7 meters). • Given by E = h = hc/ What is the energy of one photon of light with  = 630 nm? • Short wavelengths ()  high energy; e.g., X rays - very dama in to life e X-rays damaging hc (6.63 X 10 - 34 J s)(3.0 X 10 8 m/s) • Long wavelengths ()  low energy; E  hν   e.g., radio waves - safe λ (6.3 X 10 - 7 m)  3.16 X 10 -19 J Electromagnetic Spectrum ATOMIC SPECTRA Radio waves Experimental observations of the interaction of Some Facts radiation with matter. Microwave Inverse relationship Atom + h Atom* absorption Infrared between  and  Atom* Atom + h emission Visible  (lambda) ranges from 1013 to 10-3 nm Atoms absorb and emit light with discrete energy Ultraviolet (’s and ’s). They can have only particular  (nu) ranges from amounts of energy – energy of atoms is quantized. 104 Hertz (Hz) to X-rays 1020 Hz Energy levels of atoms - it's the electrons that Gamma rays are important - energy levels of the electrons.   5
  • 6. Atomic Spectrum of Hydrogen Atoms Simplest element, it has the simplest spectrum. See a series of lines in the atomic spectrum of hydrogen atoms. Only discrete ’s and ’ of li ht are absorbed O l di t ’ d ’s f light b b d or emitted by hydrogen atoms. This resulting spectrum is unique for hydrogen - different from all other elements. Experiment to View the Atomic Spectrum of H Atomic Spectra of Hydrogen Numerous lines ranging from the ultraviolet ( < 400 nm) to the infrared region ( > 800 nm). Figure 7.6 J. J. Balmer (1885): Studied the lines in the visible portion of the the spectrum (400 nm to 700 nm). energy energy emission H2 H H* H + light Continuous Spectrum Found a simple equation ( F d i l ti (empirical) for calculating i i l) f l l ti the emission wavelengths in the visible region: 1  1 1  Figure 7.6  RH  2  2  RH = Rydberg constant λ 2 n  = 109,678 cm-1 Each type of atom (element) has its own unique spectrum (lines). n = 3, 4, 5, and 6 6
  • 7. Atomic Spectra of Hydrogen General equation for calculating all emission Will the lines in the hydrogen spectrum: photon be absorbed ? 1  1 1  RH = Rydberg constant  RH  2  2  = 109,678 cm-1 , λ n   i nf  Restriction: ni and nf are whole numbers 1st Bohr orbit If of the proper ranging from 1 to infinity. 2nd Bohr orbit energy, the photon is absorbed and the The above equation is called the Rydberg 3rd Bohr orbit electron jumps to a equation. higher energy orbit. Different Series of Spectral Lines for H atoms Absorption 1st Bohr orbit Lyman series: nf = 1; ni = 2, 3, 4,…(ultraviolet) 2nd Bohr orbit Electron can return to Balmer series: nf = 2; ni = 3, 4, 5,…(visible) 3rd Bohr orbit the ground state by Paschen series: nf = 3; ni = 4, 5, 6, …(infrared) emitting a photon of Brackett series:nf = 4; ni = 5, 6, 7, …(infrared) the same energy. EXPLANATION OF H-LINE SPECTRUM Niels Bohr (1913), Danish physicist Developed a theoretical model for the Emission hydrogen atom. Bohr viewed the electron as moving around the nucleus in only fixed (discrete) radii or orbits (planets in a solar system). 1st Bohr orbit This placed restrictions on the sizes of the orbits 2nd Bohr orbit and the energy that the electron can have in a 3rd Bohr orbit given orbit (departure from classical physics). 7
  • 8. Potential Energy Figure 7.9 Bohr described the potential energy of the Bohr’s Model of H-atom electron in the hydrogen atom by a simple (?) n = 1: First Bohr orbit, ground state, lowest equation: potential energy. 2 4 2π me E If the hydrogen atom in the ground state n2 h2 absorbs energy, then the electron goes to a m = mass of the electron (9 109 X 10-31 kg) (9.109 higher energy (larger) orbit (n = 2, 3, 4, ...); g gy ( g ) ( ) e = charge of the electron (1.602 X 10-19 C, called excited states. (1.519 X 10-14 kg1/2 m3/2 s-1) For transitions in the Bohr Model of the H-atom h = Planck’s constant (6.63 X 10-34 J · s) n = quantum number (1, 2, 3, ….) n = 1 to n = 2 absorbs energy 2 2π me 4 same energy R'H   2.18 X 10-18 J n = 2 to n = 1 emits energy h2 Bohr’s Hydrogen Atom Bohr’s Equation of Energy  R'  E n  - 2H  n  1, 2, 3, ...  (integers)  n  R’H: constant (2.18 X 10-18 J) n: quantum number (has values from 1 to  ) Negative sign: Potential energy of the atom < potential energy of H+ and a free electron. b  R’H Lowest energy, n = 1 (E < 0) Highest energy, n =  (E = 0)  R'  E n  - 2H  n  1, 2, 3, ...  (integers)  n  8
  • 9. Example: What is the change in energy of the hydrogen atom when the electron goes from the n = 3 to the n = 1 level ? Use the equation for the change in energy for H- atom:  1 1  ΔE  R' H  2  2 R  n n   i f   1 1 ΔE  2.18 X 10 -18 J  2  2   1.94 X 10-18 J 3 1  A photon of light energy is emitted, since ni > nf , E is negative. Figure 7.9 Energy of Transitions in Bohr H-Atom What is the frequency () and wavelength () of this photon ? Use Einstein‘s equation and solve for : Energy of the  R' H  ΔE  hν Initial State: E i   2  n    i  ΔE 1.94 X 10 -18 J ν   2.93 X 1015 Hz h 6 63 X 10 - 34 J  s 6.63  R'  Calculate wavelength () : Energy of Final E f   2H  State:  n  c  λν  f  c 3.00 X 10 8 m/s λ   1.02 X 10 - 7 m  102 nm ν 2.93 X 1015 /s Energy of Transitions in Bohr H-Atom  - R'   - R'  ΔE  E f  E i   2 H    2 H   n   n   f   i   1 1  ΔE  R' H  2  2   hν R n n   i f  If ni > nf , then a photon is emitted, E is negative. If ni < nf , then a photon is absorbed, E is positive. 9
  • 10. Relationship between Bohr’s equation and the de Broglie’s Hypothesis (1924) Rydberg equation: • If electromagnetic radiation (light) can have particle-like properties (photon), then electrons Bohr’s equation: may also possess wave-like properties. • Electrons do indeed have both particle and  1 1  ΔE  R' H  2  2  wave-like properties !!! Electrons are similar to n n  g light.  i f  • From Einstein's theory of relativity: Rydberg Equation: E  mc 2 1  1 1  m  mass  RH  2  2  c  speed of light λ n   i nf  This equation relates energy and mass. Rydberg constant calculated from Bohr’s theory: de Broglie’s Hypothesis ΔE  hv  hc 1  hc   Using photon equation for light: λ λ hc c   E  h  R' H in J   c  RH in cm 1  hc   Substitute mc2 for E and solve for : 1 2.18 X 10-18 J  1m        6.63 X 10 J  s 3.00 X 10 m/s  100 cm  - 34 8 hc mc 2   109,600 cm -1  and Agrees well with the known Rydberg constant h value (109,678 cm-1).  mc Bohr’s Theory de Broglie’s Hypothesis • Only works for the hydrogen atom; not a general theory, it is limited and incomplete. • Notice that the product, mc, is defined as momentum (i.e., mass X velocity). • Used some elements of "classical physics", which do not apply to atomic and subatomic • This equation then relates wavelength, particles !!!! mass, and velocity. • Questions for Bohr: • For an electron, its speed must be less than – Why is energy of the electron quantized? the speed of light, c. We can simply – Why are electrons restricted to only certain substitute in for the speed (velocity) of the orbits? electron, v. – Why are atoms stable (exist)? 10
  • 11. The wavelength of an electron (a particle) is given by: de Broglie Wavelength For a Baseball h  h  mv mv v  velocity (m/s) For the baseball: m v  momentum (particle property) (p p p y) Units : mass is 0.14 kg and velocity is 40 m/s kg  m 2 6.63 x 10 -34 J  s s  m (distance, wavelength)   1.2 x 10 -34 m kg  m (0.14 kg)(40 m/s) s Electrons, protons, and neutrons experience Wave properties of particles only apply to atomic diffraction - wave property !!!! and subatomic particles – not to baseballs !!!! Diffraction Pattern for Al with X-rays and Electrons QUANTUM MECHANICS (WAVE MECHANCIS) Erwin Schrödinger (1926) Nobel Prize (1933) Applies wave properties of matter to explain pp p p p atomic properties. Bohr’s theory: Electrons move around the nucleus in fixed (discrete) orbits (e.g., solar system). electrons X-rays Wave mechanics: Treats electrons as waves – Figure 7.14 difficult to perceive. Example: This theory leads to a series of mathematical Calculate the de Broglie wavelength for an functions called wave functions. electron travelling at 1 % the speed of light (3.00 X 106 m/s). The electron wave function is called an orbital h (atomic orbital). Use de Broglie’s relationship:   m v For an electron, The t Th term “orbital” i used to distinguish f “ bit l” is d t di ti i h from Bohr’s ideas of fixed orbits. m = 9.11 X 10-31 kg; v = 3.00 X 106 m/s 6.63 X 10 - 34 J  s λ  2.43 X 10 -10 m or 243 pm 9.11 X 10- 31 kg3.00 X 106 m/s  Follow the units through!!!! 11
  • 12. Interference of Waves Electron Waves Two waves with the same frequency add together if they are “in phase” (their peaks exactly match). Constructive interference. 4 wavelengths 3.6 wavelengths destructive interference Interference of Waves These electron wave functions are quantized. They must have integral numbers of Two waves with the same wavelengths, otherwise destructive interference frequency but exactly will result in annihilation of the electron wave. “out of phase” (peak of one wave matches a valley of the other wave) cancel f h h ) l out (destroyed). Energy changes in an atom - simply changes in wave functions (patterns) which are quantized. Destructive interference. Electrons exist only in those regions in which their waves reinforce each other. In wave mechanics, the electrons do not orbit the Allowed (Stable) Orbital: nucleus in fixed, circular orbits (Bohr’s ideas). 4 wavelengths – Rather, the electron wave function takes on a constructive interference particular shape, a probability of finding the electron in a particular volume of space. An atomic orbital is characterized by: Forbidden (Unstable) Orbital energy 4.5 wavelengths – size destructive interference shape orientation in space 12
  • 13. The “p” Orbitals: Are not spherical, consist of TYPES (SHAPES) OF ATOMIC ORBITALS two lobes of electron density about the nucleus. The “s” Orbitals: Have a spherical shape: The “s” Orbitals: Have a spherical shape: There are three individual “p” orbitals, differ only in their orientation in space: Figure 7.18 Figure 7.20 The three individual “p” orbitals, represented The “s” Orbitals: Have a spherical shape: in an atom: 13
  • 14. The “d” Orbitals: Have a more complex shape (four QUANTUM NUMBERS lobes of electron density about the nucleus). Five individual “d” orbitals, differ only in their • PRINCIPAL QUANTUM NUMBER (n) Determines orientation in space: the energy and size of an orbital. – Allowed values  1, 2, 3,…  (positive integers) • As n increases the energy and size of the increases, Figure 7.21 orbital increases. • All orbitals that have the same value for "n" are in the same "shell". n = 1 shell (first shell) n = 2 shell (second shell) n = 3 shell (third shell) etc. The “f” Orbitals: Have a very complex shape (eight Angular Momentum (Shape) Quantum Number (l): lobes of electron density about the nucleus). This quantum number determines the shape of There are seven individual “f” orbitals that vary the orbital. only in their orientation in space. Divides a shell into smaller groups called subshells. Only certain "l" values are possible-limited by "n": Can have integral values from zero to n – 1 (0, 1, 2, 3, (0 1 2 3 ....n - 1) Shells Subshells n=1 l=0 n=2 l = 0, 1 n=3 l = 0, 1, 2 Angular Momentum (Shape) Quantum Number (l) Typically, a letter code is used to specify the Quantum Numbers “l” values: l 0 1 2 3 4 5…. Bohr’s theory used a single quantum number (n) to describe an orbit. letter s p d f g h…. Quantum mechanics theory (wave mechanics) Letter designations  Nature of spectral has three quantum numbers (n, l, ml) to describe feature: an atomic orbital. s  Sharp-very narrow p  Principle-very strong d  Diffuse-spread out f  Fundamental 14
  • 15. Angular Momentum (Shape) Quantum Number (l) MAGNETIC QUANTUM NUMBER (ml): To designate a subshell, we need to specify • For a "d" subshell: both "n" (number) and "l" (letter): l = 2 then ml = -2, -1, 0, 1, 2 (five ml values) Shell Subshell designation n=1 l=0 1s There are five orbitals i a "d" subshell. • Th bit l in b h ll n=2 l=0 2s n=2 l=1 2p • For the "f" subshell: l = 3 then ml = -3, -2, -1, 0, 1, 2, 3 n=3 l=2 3d (seven ml values) • There are seven orbitals in a "f" subshell. Angular Momentum (Shape) Quantum Number (l) • For a given "n" value, there are small differences in energy for various "l" values. • Order of increasing energy of subshells in the same shell: s < p < d < f < g…. increasing energy 4s < 4p < 4d < 4f MAGNETIC QUANTUM NUMBER (ml) REPRESENTATION OF ORBITALS • Describes the orientation in space relative to (shapes and sizes) other orbitals of that same subshell (l). – Divides a subshell into individual orbitals. Electron wave form (function) considers a • Possible ml values :(-l, -l + 1, ....+l) probability of finding the electron around the • For the "s" subshell: nucleus. l = 0 then ml = 0 • There is only a single orbital in an “s” subshell. Define the size and shape of an orbital by a • For the "p" subshell: 90% probability diagram (90% of the electron density lies within these boundaries, 90 % l = 1 then ml = -1, 0, 1 (three ml values) chance that the electron will be found within this volume). • There are three orbitals in a "p" subshell. 15
  • 16. The “s” Orbitals: n = 1 to infinity; l = 0; ml = 0 There are three individual “p” orbitals in a “p” Have a spherical shape: subshell, differ only in their orientation in space: The “d” Orbitals: n  3; l = 2; ml = -2, -1, 0, 1, 2 Five individual orbitals in a “d” subshell. They have a more complex shape, differ only in their orientation in space. Each have the same energy, size, and 1s < 2s < 3s shape. Increasing size and energy The “p” Orbitals: Five individual “d” orbitals, differ only in their orientation in space: n  2; l = 1; ml = -1, 0, 1 Three individual orbitals in a “p” subshell. They all have the same shape, size, and energy - differ only in their orientation in space. Consist of two lobes of electron density about the nucleus. Figure 7.21 16
  • 17. THE “f” ORBITALS: MAGNETIC PROPERTIES OF THE ELECTRON n  4 ; l = 3; ml = -3,-2, -1, 0, 1, 2, 3 Seven individual orbitals in the “f” subshell. Very complex shape (8 lobes of electron density) and differ only in their orientation in space. Each have the same energy, size and shape. Orbitals with the same energy, i.e., the three p orbs, five d orbs, etc. are said to be degenerate. ELECTRON SPIN MAGNETIC PROPERTIES OF THE ELECTRON The quantized spin of the electron is It was found that atoms of some elements have verified by experiment. magnetic fields. This was explained by considering that the electron is spinning. From electromagnetic theory, a spinning charge generates a magnetic field. Hence, electrons behave like very small magnets. Figure 7.17 ELECTRON SPIN Quantum mechanics theory predicts that the A complete set of quantum numbers to electron has only two possible spin states. describe an electron’s wave form (function): Hence, electron spin is quantized. An l A electron spin quantum number ( s) i i b (m is assigned to the electron. n l ml ms ms has values of +1/2 and -1/2 These two spin states generate magnetic fields that are directly opposed. 17
  • 18. Pauli exclusion principle: States that no two electrons in an atom can have the same set of four quantum numbers. Electrons in Shells n, l, ml  specify an orbital maximum # of Shell (n) Subshells electrons 1 s 2 ms  specify electron spin 2 s, p 8 3 s, p, d 18 Consequently, no more than two electrons can 4 s, p, d, f 32 be in an orbital. If an orbital contains two electrons, then they must have opposite spin quantum numbers (ms values). Quantum Numbers Quantum (Wave) Mechanics Quantum Numbers: n l designation ml (subshell) Principal - n (energy & size of orbitals) value value values Angular Momentum - l (shape of orbitals) 1 0 1s 0 Magnetic - ml (orientation of orbitals) 2 0 2s 0 Spin - ms (spin of e-’s in orbitals) Pauli Exclusion P i i l P li E l i Principle: 2 1 2p -1, 0, 1 – No two electrons in an atom can have 3 0 3s 0 the same set of four quantum numbers 3 1 3p -1, 0, 1 – n, l, ml  specify an orbital 3 2 3d -2, -1, 0, 1, 2 – e- spin distinguishes the two e-’s in an orbital (ms) Electron Configuration (Electronic Structure) Electrons in Subshells The distribution of electrons among orbitals of # of maximum # an atom. Subshell orbitals of electrons s 1 2 Ground State electron configuration: Lowest p 3 6 energy arrangement of electrons. d 5 10 Electron configuration: List subshells that f 7 14 contain electrons and designate their populations by appropriate superscripts. 18
  • 19. Hydrogen Atom Electron Configuration Ground State electron configuration of O: 1s2 2s2 2p4 # of electrons in the subshell • Orbital Diagram: Shows each orbital by a box (circle) and how the electrons are placed in the orbitals with their spins specified. H 1e- 1s1 • s subshells fill with electron pairs; one spin up Angular Momentum and one spin down in the 1s; same for the 2s d d h f h principal (shape) quantum # • This leaves 4 electrons for the 2p subshell. quantum # (subshell) (shell) Why did we fill the This electronic structure accounts for the 2p subshell this way? observed chemical properties of the 1s2 2s2 2p4 hydrogen atom. Electron Configuration For Helium Many different ways to distribute the four electrons in the 3 individual p orbitals in the p Helium is in Group 8A, Period 1 of the Periodic subshell. Table (Atomic Number 2) # of electrons in Hund's rule: For a partially filled subshell, the subshell the lowest energy arrangement will have the maximum number of unpaired electrons (orbitals f p ( He 2e- 1s2 with only a single electron) each with the same Angular Momentum (parallel) spin state. principal (shape) quantum # quantum # (subshell) He: the first Noble Gas; inert, unreactive; Why ? 2p4 Because the n = 1 shell is filled with 2 electrons Orbital diagrams for a p subshell with 4 electrons Oxygen, Group 6A, Period 2; Element 8 It doesn’t matter how these three individual p orbitals are displayed, one orbital must have Has 8 e-’s, the n = 1 shell is filled with 2 two electrons with paired spins and two orbitals electrons, the other 6 electrons go into the must each contain one electron with parallel n = 2 shell. spin. O 8e- 1 s2 2 s2 2 p 4 These are all equivalent orbital diagrams for a p4 subshell. 19
  • 20. Orbital diagrams for a p subshell with 4 electrons MAGNETIC PROPERTIES OF ATOMS Higher energy arrangements of electrons Predict magnetic properties (diamagnetic or paramagnetic) from ground state electron configurations and orbital diagrams. Consider Nitrogen with 7 electrons: N 7e- 1s2 2s2 2p3 These are higher energy orbital diagrams for a p4 subshell. It is paramagnetic with 3 unpaired electrons. MAGNETIC PROPERTIES OF ATOMS MAGNETIC PROPERTIES OF ATOMS If all electrons in an atom are paired in orbitals (i.e., orbitals are filled), then the magnetic C moments (fields) of the electrons exactly cancel. 6e- The atom will not be affected (attracted) by a magnet. The atom is said to be diamagnetic. 1s2 2s2 2p2 p paramagnetic with 2 unpaired electrons g p diamagnetic Al 13 e- 1s2 1s2 2s2 2p6 3s2 3p1 e.g., Helium (He - 2e-) paramagnetic with 1 unpaired electron MAGNETIC PROPERTIES OF ATOMS MAGNETIC PROPERTIES OF ATOMS If an atom has a subshell that is partially filled, then the magnetic moments of "unpaired" It has no unpaired Be electrons will add together to make the atom electrons, so it is 4e- magnetic. The atom will be attracted by a diamagnetic. magnet. It is said to be paramagnetic. 1s2 2s2 H paramagnetic Ne 10e- 1s1 1s2 2s2 2p6 Oxygen Paramagnetic, 2 unpaired e-’s diamagnetic with no unpaired electrons 1s2 2s2 2p4 20
  • 21. Ground-state electron configurations for atoms with many electrons: Fill orbitals by energy, lowest energy orbitals (subshells) are filled according to: 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p “Aufbau principle”: German for “building up”; put electrons into the lowest energy orbitals. A simple way to remember this order: Set S t up th s subshells the b h ll in a column, then the p subshells in a column next to it, then the d subshells in a column next to it, etc. Figure 7.23 Then fill along the diagonals of the column Figure 7.24 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p 21
  • 22. An Example for a Many Electron Atom Filled shells yield particularly stable electron Consider Iron, Atomic Number 26 (# of protons) configurations, e.g., the noble gases: He 2e- 1s2 26Fe  26 e- Ne 10e- 1s2 2s2 2p6 Electron Configuration: Fill the subshells Ar 18e- 1s2 2s2 2p6 3s2 3p6 according to their energy: K 36e- 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 Kr We will be concerned with the outer-shell 1s2 2s2 2p6 3s2 3p6 4s2 3d6 electrons. These are called valence electrons and they control the chemical properties of the atom. The electrons in the inner-shells are called the core electrons. The have little effect on chemical properties. What are the magnetic properties for this ABBREVIATED ELECTRON CONFIGURATIONS electron configuration of Fe?? Focus on the 3d subshell (five orbitals, partially The noble gas core will be indicated by the filled subshell). appropriate noble gas element symbol in brackets followed by the additional electrons: Fe 1s2 2s2 2p6 3s2 3p6 4s2 3d6  [Ar] 4s2 3d6 3d6 For the halogens in Group 7A: F [He] 2s2 2p5 Fe - Paramagnetic with four unpaired electrons. Cl [Ne] 3s2 3p5 Br [Ar] 4s2 3d10 4p5 Electron configurations of the elements are Use the periodic table to determine the last listed in Table 7.3 (page 300). subshell that is being filled: Some exceptions to our guidelines-we will ignore Groups 1A and 2A s subshells these exceptions. Groups 3A to 8A p subshells For example: Chromium (Cr-24 e-) F mp m um ( 1s 2 2s2 2p6 3s2 3p6 4s2 3d4 expected Transition metals d subshells 1s2 2s2 2p6 3s2 3p6 4s1 3d5 actual Lanthanides f subshells For example: Copper (Cu-29 e-) Actinides f subshells 1s2 2s2 2p6 3s2 3p6 4s2 3d9 expected 1s2 2s2 2p6 3s2 3p6 4s1 3d10 actual 22
  • 23. Figure 7.28 Why do elements in a group have similar chemical properties? Because they have similar valence shell (outer shell) electron configurations. Group 2A - Alkaline earths Group 7A - Halogens Be 2s2 F 2s22p5 Mg 3s2 Cl 3s23p5 Ca 4s2 Sr 5s2 Br 4s24p5 Ba 6s2 I 5s25p5 Ra 7s2 ns2 np5 ns2 23