Chemistry 285 Advanced Inorganic Chemistry

Lecture Notes Assoc. Prof. Joel R. Salazar

Chapter 1
Atomic Structure

Common Applications of Inorganic Chemistry

How about many electron system?

Polyelectronic Atom
Semi-empirical Method and Ab initio Approximations : Hartree Fock Method (SCF) Assumptions 1.) one reasonable for each electron 2.) shielding or screening Note: these assumptions are used to explain periodic properties: a.) radius b.) electron affinity c.) ionization energy d.) electronegativity

Hartree Fock SCF Orbitals

Iterative method for solving the many-electron Schrdinger equation developed by D.R. Hartree (1928)

Effective Nuclear Charge

Sample Problem
What is the Zeff for P15

Ans: Zeff = 4.8

Sample Problem
2.) Calculate the Ionization energy for 13 Al. Al =1s2 (2s2p)8 3s23p1 13 Ans. 10.73 Kj

Solution
Alo = 1s2 (2s2p)8 (3s2 3po) = 2(0.35) + 8 (0.85) +2 (1.0) = 9.5 Al+ = 1s2 (2s2p)8 (3s1 ) = 1(0.35) + 8 (0.85) + 2(1.0) = 9.15 B.E. = 13.6 (Z /n)2 B.E.Al (o) = 3 (13.6) (13 9.5/3)2 = 55.53 B.E.Al(+) = 2 (13.6) (13 9.15/3)2 = 44.80 I.E. = B.E. (Alo) - B.E.(Al+) = 10.73 Kj

What is the Zeff for Nickel 3d and 4s 3d = 7.55 4s = 4.05

Atomic Energy States

Term symbols: a shorthand notation that describes the
electron distribution in atoms or ions, i.e. the ml and ms quantum numbers. Spectroscopists most frequently use these.

Microstate = defined as the different ways of putting the electrons in orbitals while taking into account the electron electron repulsion

The result of calculation is called Russell Saunders coupling and presented as an atomic term symbol

Spin- orbit Coupling = the spin and orbital angular momenta of individual electrons are strongly coupled together

The possible term symbols for various electron configuration

Electron Configuration s1 p1 p2 and p4 p3 p1 and p5 d1 andd9 d2 and d8 d3 and d7 d4 and d6 d5 Term Symbol 2 S (2) 2 P (6) 1 S,1D,3P (15) 2 P,2D, 4S (20) 2 P (6) 2 D (10) 1 S,1D,1G,3P,3F (45) 2 P,2D,2F,2G,2H,4P,4F

Terms for Equivalent electrons

Terms

for configuration P6-n is the same as pn (p4 and p2; p1 and p5; p3 and p6) D10-n is the same as dn ( d1 and d9, d2 and d8 etc.)

Term Symbols for nd2

Term
1 3 1 3 1

Number of State 9x1 =9 7x3 =21 5x1 =5 3x3 =9 1x1 =1 Total =45 (microstates)

F D

P S

Multiplicity
s1

l = 0 and s = Term Symbol : 2S 2S +1 = 2(1/2) + 1 =2 p1 l =1 and s = 2S + 1 = 2 (1/2) + 1 = 2 Term Symbol : 2P s1p1 parallel (3P)and antiparallel (1P)

Microstates (d2)
1 1.) _ _ _ _ L=4 G 3 2.) I I _ _ _ L=3 F 1 3.) _ _ _ _ L=2 D 3 4.) _ I I _ _ L=1 P 1 5.) _ _ _ _ L=0 S What is the ground term of the configurations 3d5 of Mn2+ and 3d3 of Cr3+ Ans. 6S and 4F

The ML and Ms are tabulated in array

1 1 2 1 ML 1 3 1 1 2 1 1 -1 0 +1 MS Highest ML = 2 (the array ML = 2,1,0,-1,-2 exists corresponding to L = 2) These values occur for Ms = 0 A term with L = 2; S = 0 or1D 2 1 0 -1 -2

Term Symbols
The array after subtracting the microstate 1D
Ml 0 2 1 0 -1 -2 1 1 1 -1 1 2 1 1 1 1

0 1 Ms From the highest remaining ML = 1 The array ML = -1, 0, +1+ exists corresponding to L =1 These values occur for Ms = 1, 0 ,-1 L = 1; and S = 1 or 3P

Term Symbols
The array after subtracting the microstate 3P
2 1 0 -1 -2 -1 0 Ms 1

Ml

Ml =0 and MS = 0 and 1S

Sample Problem
Use Hunds rules to deduce the lowest energy state of an excited state of a Be atom whose electron configuration is 1s2 2s1 3s1 and of the ground state of a carbon atom 1s22s22p2 Ans: 3S1
3

Po

Sample Problem
Identifying

Ground State Ans. 3F2 Ans. 6S5/2 Ans. 3F4

3d2

3d5

3d8

Sample problem
Show

that the term symbol corresponding to an nd10 electron configuration is 1So

Note : Same as ns2 and np6

Sample Problem
Deduce

the values of J associated with the term symbols 2S, 3D and 4F.

Problem Set 1

1.) a.) Determine the number of microstates associated with electron configuration p1d1 b.) Find out all the term symbols for this electron configuration

The Periodic Table

Lanthanide contraction
Note

that although there is a significant increase in radius in going from the 3d to the 4d metals, the 4d and 5d metals are remarkably similar in size a result of Lanthanide contraction

Electron Affinity = the energy change associated with the

process in which the electron is added to a gaseous atom.

A(g) + e- ==== A-(g)

Measuring Electronegativity
1.) Mulliken Electronegativity Assumption: if the atoms I and EA are both low, then the atom will tend to lose electrons than gain them M = 1/2 (I + EA) Conversion between Pauling and Mulliken electronegativity P = 1.35 (M)1/2 1.37 2.) Allred Rochow Definition Assumption: Elements with high electronegativity are those with high effective nuclear charge and with smaller covalent radius AR = 0.744 + 35.90 Zeff/ (r/pm)2

Polarizability ()
Polarizability of an atom is its ability to be distorted by an electric field( such as that of the neighboring ion) A polarizable atom or ion is one with orbitals that lie close in energy Polarizability is likely to be high if the separation of the frontier orbitals is small Large, heavy atoms and ions tend to be highly polarizable (closely separated frontier orbital)

Sample Problem
Which would be the more polarizable: an F- an I- ion? Which would be more polarizing, Na+ or Cs+? Species that effectively distort the electron distribution of a neighboring atom or anion are described as having polarizing ability. Fajans Rule (factors that affect polarization) 1.) Small, highly charged cations have polarizing ability 2.) Large, highly charged anions are easily polarized 3.) Cations that do not have a noble gas electron configuration are easily polarized (important for d block element)