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Quantum Theory and the
Electronic Structure of Atoms
Properties of Waves




Wavelength (l) is the distance between identical points on
successive waves.

Amplitude is the vertical distance from the midline of a
wave to the peak or trough.
                                                             7.1
Properties of Waves




Frequency (n) is the number of waves that pass through a
particular point in 1 second (Hz = 1 cycle/s).

             The speed (u) of the wave = l x n
                                                           7.1
Maxwell (1873), proposed that visible light consists of
electromagnetic waves.


                                         Electromagnetic
                                         radiation is the emission
                                         and transmission of energy
                                         in the form of
                                         electromagnetic waves.




        Speed of light (c) in vacuum = 3.00 x 108 m/s

                 All electromagnetic radiation
                            lxn=c
                                                                 7.1
z             Electric field component
              y




                                                 x


Magnetic field component
x
z   Electric field component




                               x
z   Electric field component




                               x
x
y




                           x


Magnetic field component
y




                           x


Magnetic field component
z             Electric field component
              y




                                                 x


Magnetic field component
7.1
A photon has a frequency of 6.0 x 104 Hz. Convert
  this frequency into wavelength (nm). Does this frequency
  fall in the visible region?

                                       l
lxn=c
  l = c/n                          n
  l = 3.00 x 108 m/s / 6.0 x 104 Hz
  l = 5.0 x 103 m
  l = 5.0 x 1012 nm



                     Radio wave

                                                        7.1
Mystery #1, “Black Body Problem”
Solved by Planck in 1900

Energy (light) is emitted or
absorbed in discrete units
(quantum).



                               E=hxn
                               Planck’s constant (h)
                               h = 6.63 x 10-34 J•s


                                                       7.1
Mystery #2, “Photoelectric Effect”
                                     hn
Solved by Einstein in 1905

   Light has both:
                                          KE e-
   1. wave nature
   2. particle nature


Photon is a “particle” of light




                                                  7.2
When copper is bombarded with high-energy electrons,
   X rays are emitted. Calculate the energy (in joules)
   associated with the photons if the wavelength of the X
   rays is 0.154 nm.


E=hxn
E=hxc/l
E = 6.63 x 10-34 (J•s) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m)
E = 1.29 x 10 -15 J




                                                                7.2
Line Emission Spectrum of Hydrogen Atoms




                                           7.3
Fig. 7.p267middle
7.3
Bohr’s Model of
   the Atom (1913)
1. e- can only have specific
   (quantized) energy
   values
2. light is emitted as e-
   moves from one energy
   level to a lower energy
   level
                   1
      En = -RH (        )
                   n2

n (principal quantum number) = 1,2,3,…
RH (Rydberg constant) = 2.18 x 10-18J
                                         7.3
E = hn




E = hn




                  7.3
Why is e- energy quantized?




De Broglie (1924) reasoned
that e- is both particle and
wave.
   2pr = nl   l = h/mu
    u = velocity of e-
     m = mass of e-

                                 7.4
What is the de Broglie wavelength (in nm)
    associated with a 2.5 g Ping-Pong ball
    traveling at 15.6 m/s?



l = h/mu      h in J•s m in kg u in (m/s)
l = 6.63 x 10-34 / (2.5 x 10-3 x 15.6)
l = 1.7 x 10-32 m = 1.7 x 10-23 nm




                                                7.4
Chemistry in Action: Element from the Sun

In 1868, Pierre Janssen detected a new dark line in the solar
emission spectrum that did not match known emission lines
            Mystery element was named Helium

In 1895, William Ramsey discovered helium in a mineral of
uranium (from alpha decay).
Schrodinger Wave Equation
In 1926 Schrodinger wrote an equation that
described both the particle and wave nature of the e-
Wave function (Y) describes:
  1. energy of e- with a given Y
  2. probability of finding e- in a volume of space
Schrodinger’s equation can only be solved exactly
for the hydrogen atom. Must approximate its
solution for multi-electron systems.



                                                      7.5
Schrodinger Wave Equation
    Y = fn(n, l, ml, ms)

principal quantum number n

n = 1, 2, 3, 4, ….

distance of e- from the nucleus



         n=1     n=2         n=3



                                     7.6
Where 90% of the
e- density is found
for the 1s orbital




  e- density (1s orbital) falls off rapidly
  as distance from nucleus increases




                                              7.6
Schrodinger Wave Equation
                   Y = fn(n, l, ml, ms)
       angular momentum quantum number l
      for a given value of n, l = 0, 1, 2, 3, … n-1


                                 l=0      s orbital
       n = 1, l = 0
                                 l=1      p orbital
     n = 2, l = 0 or 1
                                 l=2      d orbital
   n = 3, l = 0, 1, or 2
                                 l=3      f orbital
Shape of the “volume” of space that the e- occupies

                                                      7.6
l = 0 (s orbitals)




                     l = 1 (p orbitals)




                                          7.6
l = 2 (d orbitals)




                     7.6
Schrodinger Wave Equation

           Y = fn(n, l, ml, ms)

    magnetic quantum number ml

          for a given value of l
           ml = -l, …., 0, …. +l

     if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

  orientation of the orbital in space

                                                7.6
ml = -1             ml = 0            ml = 1




ml = -2      ml = -1   ml = 0   ml = 1      ml = 2
                                                  7.6
Schrodinger Wave Equation


Y = fn(n, l, ml, ms)
spin quantum number ms
ms = +½ or -½



                         ms = +½   ms = -½



                                             7.6
Oven




Detecting screen
                   Magnet


                            Slit screen
Oven




Detecting screen
                   Magnet


                            Slit screen
Oven
                        Atom beam




Detecting screen
                   Magnet


                                    Slit screen
Oven
                        Atom beam

       ms = + 1
              –
              2

Detecting screen
                   Magnet


                                    Slit screen
ms = – 1
               –
               2                                  Oven
                        Atom beam




Detecting screen
                   Magnet


                                    Slit screen
ms = – 1
               –
               2                                  Oven
                        Atom beam

       ms = + 1
              –
              2

Detecting screen
                   Magnet


                                    Slit screen
Schrodinger Wave Equation
                  Y = fn(n, l, ml, ms)
Existence (and energy) of electron in atom is described
by its unique wave function Y.
Pauli exclusion principle - no two electrons in an atom
can have the same four quantum numbers.



                Each seat is uniquely identified (E, R12, S8)
                Each seat can hold only one individual at a
                time

                                                            7.6
7.6
Schrodinger Wave Equation
                    Y = fn(n, l, ml, ms)

Shell – electrons with the same value of n

Subshell – electrons with the same values of n and l

Orbital – electrons with the same values of n, l, and ml

          How many electrons can an orbital hold?

            If n, l, and ml are fixed, then ms = ½ or - ½

            Y = (n, l, ml, ½) or Y = (n, l, ml, -½)
            An orbital can hold 2 electrons                 7.6
How many 2p orbitals are there in an atom?
n=2
        If l = 1, then ml = -1, 0, or +1
 2p
        3 orbitals
l=1



 How many electrons can be placed in the 3d
 subshell?
 n=3    If l = 2, then ml = -2, -1, 0, +1, or +2
  3d    5 orbitals which can hold a total of 10 e-

  l=2                                                7.6
Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n




                                  n=3

                     n=2
                                        1
                           En = -RH (        )
                                        n2



           n=1

                                                    7.7
Energy of orbitals in a multi-electron atom
         Energy depends on n and l




                                         n=3 l = 2

                            n=3 l = 1
                n=3 l = 0

                            n=2 l = 1
                n=2 l = 0




                n=1 l = 0
                                                7.7
“Fill up” electrons in lowest energy orbitals (Aufbau principle)




                      ??

                                 Be3 electrons
                                 Li 54 electrons
                                 C
                                 B6
                                 BBe 1s222s2 1
                                   Li 1s 2s1
                                     1s22s22p


                    H 12 electrons
                    He electron

                     He 1s12
                     H 1s
                                                              7.7
The most stable arrangement of electrons
in subshells is the one with the greatest
number of parallel spins (Hund’s rule).




                  Ne
                  F 8
                  O 7 electrons
                  N 6 electrons
                  C 9 10 electrons
                  Ne 1s22s22p56
                  C 1s22s22p
                  N
                  O
                  F     2  2   3
                               2
                               4




                                            7.7
Order of orbitals (filling) in multi-electron atom




1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
                                                            7.7
Electron configuration is how the electrons are
distributed among the various atomic orbitals in an
atom.
                                    number of electrons
                                  in the orbital or subshell
                            1s1
        principal quantum         angular momentum
            number n              quantum number l


                    Orbital diagram

                       H
                                  1s1
                                                               7.8
What is the electron configuration of Mg?
   Mg 12 electrons
   1s < 2s < 2p < 3s < 3p < 4s
   1s22s22p63s2      2 + 2 + 6 + 2 = 12 electrons
   Abbreviated as [Ne]3s2      [Ne] 1s22s22p6


What are the possible quantum numbers for the
last (outermost) electron in Cl?
 Cl 17 electrons     1s < 2s < 2p < 3s < 3p < 4s
 1s22s22p63s23p5      2 + 2 + 6 + 2 + 5 = 17 electrons
 Last electron added to 3p orbital

 n=3     l=1      ml = -1, 0, or +1   ms = ½ or -½
                                                     7.8
Outermost subshell being filled with electrons




                                                 7.8
Quntum Theory powerpoint
1s

     2s

     3s

     4s

     5s

     6s

     7s
1s

2p

3p

4p

5p

6p
3d

     4d

     5d

6d
4f

5f
1s                            1s

     2s                  2p

     3s                  3p

     4s        3d        4p

     5s        4d        5p

     6s        5d        6p

     7s   6d


                    4f

                    5f
7.8
Paramagnetic         Diamagnetic
unpaired electrons   all electrons paired


      2p                     2p
                                            7.8

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Quntum Theory powerpoint

  • 1. Quantum Theory and the Electronic Structure of Atoms
  • 2. Properties of Waves Wavelength (l) is the distance between identical points on successive waves. Amplitude is the vertical distance from the midline of a wave to the peak or trough. 7.1
  • 3. Properties of Waves Frequency (n) is the number of waves that pass through a particular point in 1 second (Hz = 1 cycle/s). The speed (u) of the wave = l x n 7.1
  • 4. Maxwell (1873), proposed that visible light consists of electromagnetic waves. Electromagnetic radiation is the emission and transmission of energy in the form of electromagnetic waves. Speed of light (c) in vacuum = 3.00 x 108 m/s All electromagnetic radiation lxn=c 7.1
  • 5. z Electric field component y x Magnetic field component
  • 6. x
  • 7. z Electric field component x
  • 8. z Electric field component x
  • 9. x
  • 10. y x Magnetic field component
  • 11. y x Magnetic field component
  • 12. z Electric field component y x Magnetic field component
  • 13. 7.1
  • 14. A photon has a frequency of 6.0 x 104 Hz. Convert this frequency into wavelength (nm). Does this frequency fall in the visible region? l lxn=c l = c/n n l = 3.00 x 108 m/s / 6.0 x 104 Hz l = 5.0 x 103 m l = 5.0 x 1012 nm Radio wave 7.1
  • 15. Mystery #1, “Black Body Problem” Solved by Planck in 1900 Energy (light) is emitted or absorbed in discrete units (quantum). E=hxn Planck’s constant (h) h = 6.63 x 10-34 J•s 7.1
  • 16. Mystery #2, “Photoelectric Effect” hn Solved by Einstein in 1905 Light has both: KE e- 1. wave nature 2. particle nature Photon is a “particle” of light 7.2
  • 17. When copper is bombarded with high-energy electrons, X rays are emitted. Calculate the energy (in joules) associated with the photons if the wavelength of the X rays is 0.154 nm. E=hxn E=hxc/l E = 6.63 x 10-34 (J•s) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m) E = 1.29 x 10 -15 J 7.2
  • 18. Line Emission Spectrum of Hydrogen Atoms 7.3
  • 20. 7.3
  • 21. Bohr’s Model of the Atom (1913) 1. e- can only have specific (quantized) energy values 2. light is emitted as e- moves from one energy level to a lower energy level 1 En = -RH ( ) n2 n (principal quantum number) = 1,2,3,… RH (Rydberg constant) = 2.18 x 10-18J 7.3
  • 22. E = hn E = hn 7.3
  • 23. Why is e- energy quantized? De Broglie (1924) reasoned that e- is both particle and wave. 2pr = nl l = h/mu u = velocity of e- m = mass of e- 7.4
  • 24. What is the de Broglie wavelength (in nm) associated with a 2.5 g Ping-Pong ball traveling at 15.6 m/s? l = h/mu h in J•s m in kg u in (m/s) l = 6.63 x 10-34 / (2.5 x 10-3 x 15.6) l = 1.7 x 10-32 m = 1.7 x 10-23 nm 7.4
  • 25. Chemistry in Action: Element from the Sun In 1868, Pierre Janssen detected a new dark line in the solar emission spectrum that did not match known emission lines Mystery element was named Helium In 1895, William Ramsey discovered helium in a mineral of uranium (from alpha decay).
  • 26. Schrodinger Wave Equation In 1926 Schrodinger wrote an equation that described both the particle and wave nature of the e- Wave function (Y) describes: 1. energy of e- with a given Y 2. probability of finding e- in a volume of space Schrodinger’s equation can only be solved exactly for the hydrogen atom. Must approximate its solution for multi-electron systems. 7.5
  • 27. Schrodinger Wave Equation Y = fn(n, l, ml, ms) principal quantum number n n = 1, 2, 3, 4, …. distance of e- from the nucleus n=1 n=2 n=3 7.6
  • 28. Where 90% of the e- density is found for the 1s orbital e- density (1s orbital) falls off rapidly as distance from nucleus increases 7.6
  • 29. Schrodinger Wave Equation Y = fn(n, l, ml, ms) angular momentum quantum number l for a given value of n, l = 0, 1, 2, 3, … n-1 l=0 s orbital n = 1, l = 0 l=1 p orbital n = 2, l = 0 or 1 l=2 d orbital n = 3, l = 0, 1, or 2 l=3 f orbital Shape of the “volume” of space that the e- occupies 7.6
  • 30. l = 0 (s orbitals) l = 1 (p orbitals) 7.6
  • 31. l = 2 (d orbitals) 7.6
  • 32. Schrodinger Wave Equation Y = fn(n, l, ml, ms) magnetic quantum number ml for a given value of l ml = -l, …., 0, …. +l if l = 1 (p orbital), ml = -1, 0, or 1 if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2 orientation of the orbital in space 7.6
  • 33. ml = -1 ml = 0 ml = 1 ml = -2 ml = -1 ml = 0 ml = 1 ml = 2 7.6
  • 34. Schrodinger Wave Equation Y = fn(n, l, ml, ms) spin quantum number ms ms = +½ or -½ ms = +½ ms = -½ 7.6
  • 35. Oven Detecting screen Magnet Slit screen
  • 36. Oven Detecting screen Magnet Slit screen
  • 37. Oven Atom beam Detecting screen Magnet Slit screen
  • 38. Oven Atom beam ms = + 1 – 2 Detecting screen Magnet Slit screen
  • 39. ms = – 1 – 2 Oven Atom beam Detecting screen Magnet Slit screen
  • 40. ms = – 1 – 2 Oven Atom beam ms = + 1 – 2 Detecting screen Magnet Slit screen
  • 41. Schrodinger Wave Equation Y = fn(n, l, ml, ms) Existence (and energy) of electron in atom is described by its unique wave function Y. Pauli exclusion principle - no two electrons in an atom can have the same four quantum numbers. Each seat is uniquely identified (E, R12, S8) Each seat can hold only one individual at a time 7.6
  • 42. 7.6
  • 43. Schrodinger Wave Equation Y = fn(n, l, ml, ms) Shell – electrons with the same value of n Subshell – electrons with the same values of n and l Orbital – electrons with the same values of n, l, and ml How many electrons can an orbital hold? If n, l, and ml are fixed, then ms = ½ or - ½ Y = (n, l, ml, ½) or Y = (n, l, ml, -½) An orbital can hold 2 electrons 7.6
  • 44. How many 2p orbitals are there in an atom? n=2 If l = 1, then ml = -1, 0, or +1 2p 3 orbitals l=1 How many electrons can be placed in the 3d subshell? n=3 If l = 2, then ml = -2, -1, 0, +1, or +2 3d 5 orbitals which can hold a total of 10 e- l=2 7.6
  • 45. Energy of orbitals in a single electron atom Energy only depends on principal quantum number n n=3 n=2 1 En = -RH ( ) n2 n=1 7.7
  • 46. Energy of orbitals in a multi-electron atom Energy depends on n and l n=3 l = 2 n=3 l = 1 n=3 l = 0 n=2 l = 1 n=2 l = 0 n=1 l = 0 7.7
  • 47. “Fill up” electrons in lowest energy orbitals (Aufbau principle) ?? Be3 electrons Li 54 electrons C B6 BBe 1s222s2 1 Li 1s 2s1 1s22s22p H 12 electrons He electron He 1s12 H 1s 7.7
  • 48. The most stable arrangement of electrons in subshells is the one with the greatest number of parallel spins (Hund’s rule). Ne F 8 O 7 electrons N 6 electrons C 9 10 electrons Ne 1s22s22p56 C 1s22s22p N O F 2 2 3 2 4 7.7
  • 49. Order of orbitals (filling) in multi-electron atom 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s 7.7
  • 50. Electron configuration is how the electrons are distributed among the various atomic orbitals in an atom. number of electrons in the orbital or subshell 1s1 principal quantum angular momentum number n quantum number l Orbital diagram H 1s1 7.8
  • 51. What is the electron configuration of Mg? Mg 12 electrons 1s < 2s < 2p < 3s < 3p < 4s 1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons Abbreviated as [Ne]3s2 [Ne] 1s22s22p6 What are the possible quantum numbers for the last (outermost) electron in Cl? Cl 17 electrons 1s < 2s < 2p < 3s < 3p < 4s 1s22s22p63s23p5 2 + 2 + 6 + 2 + 5 = 17 electrons Last electron added to 3p orbital n=3 l=1 ml = -1, 0, or +1 ms = ½ or -½ 7.8
  • 52. Outermost subshell being filled with electrons 7.8
  • 54. 1s 2s 3s 4s 5s 6s 7s
  • 56. 3d 4d 5d 6d
  • 57. 4f 5f
  • 58. 1s 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 5d 6p 7s 6d 4f 5f
  • 59. 7.8
  • 60. Paramagnetic Diamagnetic unpaired electrons all electrons paired 2p 2p 7.8