CHAPTER 10: Atomic Structure and Atomic Spectra I. The Hydrogenic Atoms (one electron species).

H, He+1, Li2+, A. Clues from Line Spectra. Reminder: fundamental equations of spectroscopy:

Photon = h
energy of photon freq of photon

relation of energy of photon to its

c
1

relation of frequency to

definition of wavenumber (units usually cm-1)

When system (atom, oscillator, rotor, etc.) interacts with light and jumps from one state to another:

Photon = E
E

spacing between energy levels

photon = E emission

photon = E
absorption The pattern of emission lines from atomic hydrogen were fit by Rydberg equation:
1 1 = RH ; RH = 109,677 cm-1 2 2 n1 n2
_

Balmer Series Lyman Paschen

n1=2 n1=1 n1=3

n2=3,4,5 n2=2,3,4 n2=4,5,6,7

Now know that n1, n2 are quantum levels n1 = lower level n2 = upper level Level spacings

E = E n 2 E n1 = photon = h =

E = hc

hc = hc

1 1 E = hcR H 2 2 n1 n 2 That Rydberg Eqn has two terms, and knowing that emissions are a result of transitions between two quantum energy levels, implies that energy levels of Hydrogen are given by an expression of the form:
En cons tan t n2

where the denominator contains the quantum number n B. The Quantum Mechanical Structure of Hydrogenic Atoms. 1. Treat just like rigid rotor, but now radial dimension can vary. Place origin at center of mass. Since nuclear mass mN>>me (electron), center of mass is virtually at nucleus.

charge +Ze Z=1 Hydrogen Z=2 He+1 e charge -e nucleus virtually at origin 2
-

Reduced mass

mNme me mN + me

2 particle problem reduced to effective 1 particle problem: An e- with effective mass me traveling around origin. 2. Schrodinger Equation

2 H = + V ( r) = E 2 2 2 just like rigid rotor Hamiltonian 2 except radial portion 0 anymore.

Kinetic energy operator Also potential energy operator V is no longer zero, but depends on radial coordinate (r=distance between nucleus and electron)

V ( r) =

Ze 2 4 o r

Coulombs Law between point charges +Ze and -e at a separation distance of r.

3.

O = vacuum permittivity = 8.85 x 10-12 J-1 c2 m-1

Solution (wave functions of H atom). Is obtained by technique of separation of variables which is made possible by the centrosymmetric potential.

n,,m = Rn, r Y,m ,

3 quantum #s radial part of wave fct

()

( )
spherical harmonics, as before

n = principal q.n. = 1,2,3,4 = angular mom. q.n. = 0,1,2 (n-1) m = magnetic q.n. = - ,0,+

4.

The angular wave equation for Y looks like something we have seen before containing the legendrian operator:
Y,m (, ) = ( + 1)Y,m (, )

5.

The radial wave equation to solve looks like this:

2 d 2 rR(r) + Veff rR(r) = ErR(r) 2 dr 2 where : Ze 2 ( + 1) 2 Veff = + 4 o r 2r 2

Note that only the radial portion contains the energy eigenvalue E, meaning the energy is fully determined by the radial part. The first term in the effective potential Veff is simply Coulombs law potential energy term. The second term is the centrifugal effect which keeps the electron from getting too close to the nucleus. This in turn depends on the amount of angular momentum of the electron about the nucleus and so depends on the quantum number.

6.

Energies (depend only on principal q# n in hydrogenic atoms)

En =

Z 2e 4 1 2 32 2o 2 n 2
e4/ 32 22 2 is the part that never varies, totally constants o

also me so it hardly varies as one goes from H to He+ to Li2+ etc.

En =

Z 2 (constan t ) n2

For hydrogen Z=1

En = 13.598 eV 2.170 1018 J = n2 n2

For others, He+, Li+2

En = Z 2 13.6 eV n2

where Z = atomic # of nucleus

7.

Atomic orbital nomenclature. The wavefunctions n,,m are called atomic orbitals. Each orbital is defined by 3 quantum #s.
Orbital name

1s 2s 2p (3 of them) 3s 3p 3d (5 of them)

n 1 2 2 3 3 3

0 0 1
0 1 2

m 0 0 -1 0 +1 0 -1 0 +1 -2 -1 0 1 2
5

s p d f 8.

=0 =1 =2 =3

e.g. 4f (then n = 4 and =3)

Degeneracy. 1 Lots of degeneracy, since E n2

E does not depend on ,m for H

(n, ,m)

(3,0,0) (3,1,-1) (3,1,0) (3,1,1) (3,2,-2) (3,2,-1) (3,2,0) (3,2,1) (3,2,2) 3d

Energy

3p (2,0,0) (2,1,-1) (2,1,0) (2,1,1) 2p (1,0,0)

9.

Shells and subshells

10. Ionization Energy

ionization E = E En=1 0 (-13. eV) = 13.6 eV Now lets see what looks like. 11. The Radial Wave function.

Rn, ( r)

Atkins replaces r variable with related variable where:

2Z r n me ao

this ratio is .99946 for H and even closer to 1.0000 for heavier nuclei

So:

2Zr nao

where ao = Bohr radius = 52.947 pm =

2 4o e2

Rn, = N n,l L n, ( )e / 2 where L n, are associated Laguerre polynomials

R(r) = (norm const)x(polynomial in r)x(decaying exponential in r)

Written as function of radial coordinate r:

Rn, = R10 r = R1s R20 r = R2s

()

Z 3 / 2 Zr / a o = 2e ao
3/2 1 Z Zr Zr / ao = 2 e ao 2 2 ao

()

12. Visualizing the s orbitals. s orbitals have spherical symmetry and have radial nodes when n>1. Convenient to describe 2 in terms of 90% boundary surfaces. i.e. sphere that enclose 90% of probab. distribution Also define mean radius of orbital as <r> (see Eq(10.19))
r = =

r d
2 3 2

r R dr d d sin Y
0 0 0

radial

Also can talk about radial distribution fct

P(r)dr = 4 r 2 2 dr
which gives probability of finding electron in a shell of thickness dr at a distance r from nucleus.

Here is for 1s:

10

13. Electron dot density diagrams:

11

14. Visualizing the p orbitals ( =1). p orbitals and beyond have non-spherical symmetry Zero amplitude at r=0 (centrifugal effect) A nodal plane The three p-orbitals m = 1,0, +1 e.g., are distinguished by quantum number

(n= 2,l=1,m l = 0) = R2,1 (r)Y1,0 (, )

Z 5 / 2 1 Zr / 2a o = r cos e 1/ 2 ao 4 (2 )
Standard practice is to construct real p-orbital s from linear comb of p orbitals, since they have complex eim in them. Thats what is usually plotted, as in the following boundary surface diagram:

Here is 3px orbital

12

Nodes summary: angular = radial = n - - 1 total = n-1

Orbital angular momentum

L= +1

15. d orbitals ( =2)

Have 2 nodal planes Again linear comb of 3d s are used to construct a set of 5 real 3d orbitals for visualizing.

Heres 3dz2

13

16. Selection rules for spectral transitions. To conserve angular momentum,

must be = 1 m must be = 0, 1

when H atom absorbs or emits light. forbidden. n can be anything. All other transition are

14

15

II.

Many-Electron Atoms (more than 1 e-). -extremely complicated due to e- -- e- repulsion -no solutions in terms of known math functions -accurate solutions available by numerical computations -solution (r1, r2, rn) = function of every e- coordinate A. The Orbital Approx. Says the wavefunction for a many-electron atom (r1, r2, rn) can be written as a product of one-electron wave functions:

(r1, r2, rn) = 1(r1), 2(r2)

(each e- occupying own orbital)

Further think of individual orbitals as hydrogenic orbitals, but with modified nuclear charges. This is starting point for mathematical treatment. Now, use hydrogenic orbitals as the basis set for describing each oneelectron orbital of the multi-electron atoms. Orbital or wave function for electron i is written as a weighted linear combination of hydrogenic atomic orbitals.
i = c1s1s + c2s2s + c2px 2px + ... where:

c1s 1s c2s 2s

is is is is

weighting coefficient H-like atom 1s but with Z>1 weighting coeff. H-like atom 2s

e.g. Heliums 2 electrons go into orbitals that are quite similar to H 1s orbitals but with 2 > Z > 1. Electron config of He = 1s2 (both in 1s-like orbitals) Each electron is interacting with a Z=+2e nucleus so He is smaller than H even though having 2 electrons. As we go to more than 2 electrons, we find that: 1s3 is excluded, i.e. is forbidden. Li = 1s22s1 2 ein 1s-like orbitals 3rd e- in a 2s-like orbital 16

The n=1 shell is said to be a closed shell once it has two electrons. We could also write the above then as: Li = [He]2s1 Pauli Exclusion Principle = no more than 2e- per orbital, and their spins must be paired. () B. Spin. Electron has 1 more degree of freedom beyond 3 spatial degrees. Intrinsic ang. Mom. Total spin q# S = 1/2 for electron, proton and neutron. This is an intrinsic quantity which cannot change. Total spin ang mom =
s s +1

Magnitude of spin about a particular axis (such as magnetic field direction in NMR) is controlled by quantum number ms, which can have possible values determined by s: ms = -s, +s So for electron: ms = -1/2 or +1/2 or

No 2 e- can have the same 4 quantum numbers.

n, ,m ,ms
i.e. be in the same quantum state.

e.g. 1s () 1s () 1, 0, 0, +1/2 1, 0, 0, -1/2 Both are in same orbital 1s but in 2 unique quantum states.

See Atkins textbook p. 338 for a more full description of Pauli Principle, and the requirement of having an antisymmetric wave function.

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C.

Penetration and Shielding. As we try to hang on to thinking about electrons of many-electron atoms occupying H-like orbitals, we are forced to introduce concept of shielding. 1. Shielding effect of e- in same s orbital is present but slight. eHe atom e-

Z=+2 Each e- is in a 1s-like orbital, but e- does not experience full +2e charge of nucleus because of the repulsive interaction with the other electron. Effective atomic # or effective nuclear charge experienced by the electrons in He = Z eff = 1.69 for He 1s electrons Zeff < Z=2 Z eff = Z - (where is shielding constant) This means each e- in He occupies 1s orbital with Z=1.69 rather than 2 or 1. (So we can substitute this Zeff for Z in the radial wave function for 1s.)

2.

Shielding of e- from the nuclear charge by e- in lower filled shells is great. 18

3.

s orbitals penetrate more to the nucleus than p orbitals because R(r) 0 at nucleus for s orbitals. Therefore, when e- -- e- repulsion is considered in many-e- atoms, 2s is below 2p in energy, rather than degenerate as in Hydrogen. 3s < 3p < 3d also.

Na 11 e3s E 2s 1s

Zeff = 2.2

Zeff = 6.85

fill 1st, lower in energy

2p

Zeff = 6.85

Zeff = 10.6

Na = 1s2 2s2 2p6 3s1 filled K shell filled L shell valence e-

E=

2.2 13.6 32

) = Zeff13.6
n2

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D.

Aufbau Principle (building up principle). 1. Order of occupation of hydrogen-like orbitals in the ground state config of many e- atoms. 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s

sneaks in under the 3d K 19 e1s22s22p63s23p64s1 instead of 3d1 4s 3s

3p 2p

3d

2s 1s

4s and 3d are very close in energy 2. 3. Feed e- into orbitals in proper succession, max of 2 e- per orbital. Hunds Rule = an atom in its ground state adopts a config with the greatest # of unpaired e- (maximum multiplicity) Why? Due to spin correlation. (Parallel spins repel each other less, causing the atom to shrink slightly, improving the electron-nuclear attraction.) e- occupy different orbitals in a subshell by energy preference. N 7 e-

2s 1s

2p subshell

keep unpaired 20

21

E.

Periodicity of Ionization Energies. 1. Minimum energy to remove e- from a many e- atom is its first ionization energy I1. Na(g) Na+ + eenergy needed = I1

I2 2nd ioniz energy, etc. IONIZATION ENERGY ~ difficulty of removing eGeneral trend I1 across row, I1 down column.

2.

Li, Na, K (alkali metals) have low I1. Have single s electron outside a filled shell, so Zeff is low.

3.

Compare Li and Be.

I1 (Be) > I1 (Li)

Plus add another 2s electron which inadequately shields the other 2s electron. 22

Zeff (2s) So I1 as Li Be 4. Now compare Be to B. I1 goes down. Why? N Be I1 B Li C O

Added e- goes into 2p (which has poor penetration toward nucleus). Nuclear charge goes up +1e, but 2p electron is well-shielded by compact 1s, 2s. 5. B C N I1 because nuclear charge is increasing, but e- are filling spatially separated 2p orbitals which poorly shield one another. B 1e in 2p -2e-2e-

C e-2e-2e-

+5

+6

6.

NO

I1 takes a dip slightly.

Now beginning to pair up e- in 2p orbitals. e- -- e- repulsion increase in that paired orbitals, and e- is easier to remove.

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F.

Electron Affinity, Eea 1. Eea = Energy released when an electron attaches to a gaseous atom. Cl(g) + e- Cl- + Eea Trends are harder to explain than ioniz. energy

G.

Numerical Computations of Many Electron Atomic Orbitals. Hartree-Fock Self-Consistent Field Theory (SCF). 1. e- -- e- repulsion is the computational problem. H = E
all electrons

2 2 Ze2 e2 i + 2m 4ori 4o

pairs

r1 = E
i,j ij

where:

all electrons

is the sum over all electrons

2 2 i 2m
Ze2 4ori

is the KE term for each electron i (easy part, separable) electron-nuclear interaction. Easy and separable.

e2 4o

pairs

r1
i,j ij

difficult part because inseparable. Involves distances 1/rij between all electrons i & j.

e- -- e- repulsion Call this Vee 24

2.

SCF: a. Simplify Vee term by allowing each e- to interact with the e- cloud formed by all other e- (i.e. 2) rather than interact with instantaneous position of the other electrons. S tart with an initial guess of the solution by putting each e- in a hydrogenic orbital using Aufbau rules. This provides 1st guess of e-cloud of each electron. Apply the approx S.E. to get improved set of orbitals. Repeat procedure until improved s are no longer changing between cycles of iteration. You have iterated to self-consistency!

b.

c. d.

3.

The electron-electron interaction really contains two effects: Coulombic repulsion Spin-spin correlation SCF solution for Na Radial distribution fct.

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