Chapter 5.

Molecular Orbitals
 Bonding in Inorganic Compounds
• Valence Bond Theory (VBT)
• Crystal Field Theory (CFT)
• Molecular Orbital Theory (MOT)

Valence Bond Theory (VBT)

Coordinatively covalent bonding by L. Pauling in 1930s
Lewis bases (ligands)
Lewis acids (metals or metal ions)
The metal utilizes hybridization of metal s, p, and d valence orbitals to
account for the observed structures and magnetic properties of
complexes.
1. Valence Bond Theory (VBT)
1916 electron pairing model by Lewis
1927 Q. M. method by W. Heitler & F. London
1930s valence bond approach by L. Pauling & J. C. Slater
HA – HB

for E (kJ/mol) & r (pm)

Resonance : minimize Eb
[H—H]+ ↔ H+H ↔ H H+

2. Molecular Orbital Theory (MOT)

bonding(1) = A(1) + B(1) bonding(2) = A(2) + B(2)
antibonding(1) = A(1) - B(1) antibonding(2) = A(2) - B(2)
 Crystal Field Theory (CFT)
1929, Hans Bethe

As originally conceived, it was a model based on a purely electrostatic

interaction between the ligands and the metal ion.

1935, modifications J.H. Van Vleck

allow some covalency in the interaction

Ligand Field Theory (LFT)

1950, apply CFT to transition metal complexes

successful in interpreting many important properties of
complexes
symmetry consideration identical to MOT
 Nature of Bonding
Electron density distribution of H2+ ion.
(ΦA+ΦB)2
ΦA2 ΦB2
ΦA2+ΦB2

A (ΦA-ΦB)2 B
Bonding M.O.  Positive overlap
i.e., e-density is higher than simple sum of e-density of
the two separated A. O. by 2ΦAΦB.
 Attraction of both nuclei for the electron is greater than
the mutual repulsion of the nuclei
 Net attraction force (Bonding Interaction)
Antibonding M.O.  Negative overlap
Shared e-density is reduced by 2ΦAΦB and internuclear
repulsion increase
 Net repulsive force (Antibonding Interaction)
 Fundamental Rules for MOT

1. M.O.는 두 개 이상의 원자가 서로 접근할 경우, interaction에 의해 orbital

overlap이 생기며, 이때 생긴 새로운 M.O.는 Linear Combination of
Atomic Orbitals (LCAO)로 나타낼 수 있다.

2. Valence electron만이 chemical bonding에 참여하며 v.e.만이 M.O.를 형

성한다.

3. Conservation of Orbital in bonding.

즉, total A.O.의 수와 전체 M.O.의 수는 같다.

4. M.O.는 A.O.와 비슷한 성질을 갖는다.

즉, Hund’s rule과 Pauli의 배타원리를 따른다.

5. 같은 symmetry property를 갖는 A.O.끼리만 서로 interaction한다.

 Fundamental Rules for MOT

6. A.O.들이 M.O.를 형성시, bonding and antibonding M.O.를 형성한다.

즉, Bonding State: 공유된 전자밀도 증가
ΦBonding = Φ1 + Φ2 (Attractive)
Antibonding State:
ΦAntibonding = Φ1 – Φ2 (Repulsive)
Nonbonding State: No overlap between A.O.

7. In M.O., there are Highest Occupied Molecular Orbital (HOMO) and Lowest
Unoccupied Molecular Orbital (LUMO).

8. Bond Order:
(# of e in Bonding M.O. - # of e in Antibonding M.O.) / 2
 “LCAO-MO”
<Linear Combination of Atomic Orbital – M.O.>
Approximates
Ψn = ∑Cnr·Φr
r
(where, Ψn = M.O. for 2e-
Cnr = Coefficient for contribution of Φr to Ψn
Φr = basis set of A.O.)

For diatomic molecule:

Ψn = C1 Φ1 + C2 Φ2
Schrödinger Eqn.:
^ = EΨ  ∑c (H-E)
HΨ ^ Φ =0
i i
Expectation Value (Average Value):
^
<Ψs |α|Ψ
<as> = s>
<Ψs |Ψs>
^ ^ |Ψ>
E= ∫ Ψ*HΨdτ
Ψ*Ψdτ
= <Ψ*|H
<Ψ*|Ψ>
 ∫(C1Φ1 + C2Φ2)* H^ (C Φ + C Φ ) dτ
1 1 2 2
∫(C1Φ1 + C2Φ2)* (C1Φ1 + C2Φ2) dτ
<Def>
Hij = ∫Φi* H^ Φj dτ
Hii = Coulomb integral dealing with e- repulsion and
kinetic energy with an orbital
Hij = Resonance integral deals with e- interaction between
orbitals (difficult to caculate)
Sij = ∫Φi* Φj dτ
Overlap integral ( coupling)
(Sii = 1 for normalized atomic orbitals)
Usually, we use real valued atomic orbitals.
Thus, Φi* = Φi & Hij = Hji & Sij = Sji

C12H11 + 2C1C2H12 + C22H22

E = C 2S + 2C C S + C 2S
1 11 1 2 12 2 22
< Variational principle >
Ci’s are chosen to minimize the calculated value of E.
EVar. ≥ E0 (Gr. St. E.)
We set ∂E ∂E
∂ C1 = 0 = ∂ C2
and solve for C1 & C2 coefficient
(C12S11 + 2C1C2S12 + C22S22) E = (C12H11 + 2C1C2H12 + C22H22)
∂ ∂
(C1 S11 + 2C1C2S12 + C2 S22) E =
2 2 (C12H11 + 2C1C2H12 + C22H22)
∂ C1 ∂ C1
(2C1S11 + 2C2S12) E = 2C1H11 + 2C2H12
i.e., C1(H11 – ES11) + C2(H12 – ES12) = 0
C1(H21 – ES21) + C2(H22 – ES22) = 0
Equivalently,
H11 – ES11 H12 – ES12
H21 – ES21 H22 – ES22 =0
“ Secular Determinant “
 (H11 – E)2 – (H12 – S12E)2 = 0 (∵ S11 = S22 = 1)

Thus, H11 + H12 H11 – H12

E1 = 1 + S12 and E2 = 1 - S12

∴ M.O. Diagram very small

E2 (neglect)

H11 H22
S=0 일때 위, 아래 같음.
S>0 S가 클수록 위가 커짐
E1 & E2
E1
ΨBonding = (1/√2)(Φ1 + Φ2)의 해
ΨAntibonding = (1/√2)(Φ1 – Φ2)의 해

H11 & H12 are tough to calculate and need approximations.

 Linear Combination of Atomic Orbitals
 = C( 1sB  1sA )
C : normalization constant  1/√2
C를 무시하고, 간단하게 표기하면

 = 1sA  1sB

a) 1sA + 1sB : + +
Z

+ 는 핵 사이의 지역에서 크다.

확률밀도( ∝ │+│2 )가 핵 사이에서 크다.
이 오비탈내의 전자는 HA & HB 를 당긴다.
→ 결합에 기여.
z –축에 대해 원통형으로 대칭인 분자오비탈을 오비탈이라 부른다.
즉, 1s = 1sA + 1sB
 Linear Combination of Atomic Orbitals

b) 1sA - 1sB : + -
Z

- 핵 사이에서 작음.
│-│2 〃 〃 〃.
(구체적으로는, HA & HB 사이의 가운데 평면
에서 - = 0 , │-│2 = 0.)
→ 결합을 붕괴시킴→ 반결합(antibonding )
오비탈이라고 부름, *로 표기
원통형 반대칭 → *
*1s = 1sA - 1sB
 Linear Combination of Atomic Orbitals

Plot of E vs. RAB → H2+ 의 위치에너지 곡선

 Linear Combination of Atomic Orbitals

H2+의 경우

두 AO의 LC (두 개의 basis functions)

→ 두 개의 선형적으로 독립인 MO가 만들어짐.
(n개의 AOs 사용 → n 〃 〃 〃)

(1s )1
H2+ 의 바닥상태 전자배치: Pauli & Hund 법칙에 따라
Homonuclear Diatomic Molecules : H2

at S=0
Linear Combination of Atomic Orbitals (LCAOs)

bonding(2) = A(2) + B(2)

antibonding(2) = A(2) - B(2)

total wave function = b(1) x b(2) = [A(1) + B(1)] x [A(2) + B(2)]

electron distribution = probability function = 2

difference between b2 & a2 = 2A x B

overlap integral = ∫ABdr = S
- Symmetry & Overlap
S > 0 : bonding
S = 0 : nonbonding overlap integral = ∫ABdr = S
-S < 0 : antibonding

- Symmetry of Molecular Orbitals

bonding antibonding
 *
π π*
 *
Molecular Orbitals from p Orbitals


M.O.s from d Orbitals
 Nonbonding Orbitals
a) Symmetry

b) E-level
 MO in Homonuclear Diatomic Molecules
bond order = 0.5 (Nb – Na)
Nb = # of bonding e; Na = # of antibonding e
i) Molecules containing 1~4 e
H2 = 1s2 B.O. = 0.5 (2-0) = 1
Homonuclear Diatomic Molecules
2pz

2px, 2py

2px, 2py

2pz
He2 = 1s21s*2 B.O. = 0.5 (2-2) = 0  not exist

He2+ = 1s21s*1 B.O. = 0.5 (2-1) = 0.5  not real

chemical but spectroscopically existence
ii) O2, F2 & Ne2
O = 1S22s22p4  B.O. = 2; paramagnetic 
mystery for life (not in VBT)
B2, C2 & N2
B = K2s22p1  B.O. = 1; diamagnetic 
However,
exp’lly paramagnetic !!!
 Secondary Mixing (Configuration Interaction)
By pictorial presentation, group orbitals of σs and σp

(-) 합성
σpz z σps
destabilization

(+) 합성
σ2s σsp
stabilization

(-) 합성
σpz* z σps*
destabilization
(+) 합성
σ2s* σsp*
stabilization
 Secondary Mixing (Configuration Interaction)
∴ M.O. E-Diagram is;

σps*
Σu σ2pz*
π*px,py πp*
σps
πpx,py πp
Σg σ2pz destabilized
p-dominent unchanged
do not overlap
with s-orbital
Σu σ2s*
σsp*
Σg σ2s
σsp

∵ M.O. of σ2s & σ2pz have same irred. rep.

i.e., they can mix (secondary mixing): Ψsp = CsΦs + C2pzΦ2pz
* Secondary mixing 결정 요소
1. s, p orbital의
overlap 정도
2. s, p orbital간의
energy gap의 크기
Orbital Mixing
M.O. energy level diagram of O2 molecule
by VBT, diamagnetic

by MOT
by Exp.
paramagnetic

HOMO

Large energy gap

No sp-hybridization
No secondary mixing
M.O. energy level diagram of N2 molecule
by VBT, sp hybridization (2s + 2pz orbital)
(with one σ & 2π bonding)

Frontier orbital
LUMO

px, py px, py

HOMO
12.4 eV

sp-hybrid

lone pair electron

 Paramagnetic O2

-183 oC O2 (l) -196 oC N2 (l)

☼ Secondary mixing 결정 요소
1. s, p orbital의 overlap 정도
2. s, p orbital간의 energy gap의 크기

< 2s-2p orbital energy gap (eV) >

E (2S) E (2P) ΔE
B -14.0 -8.3 5.7
C -19.4 -10.6 8.8
N -25.6 -13.2 12.4
O -32.3 -15.8 16.5
F -40.2 -18.6 21.6
Huge energy gap!!
∴ No secondary mixing
secondary mixing

lowering energy due to E.N.C.

 Name Bond Order Bond Length (pm)

O2+ oxonium ion 2.5 112.3

O2 dioxygen 2.0 120.07
O2- superoxide 1.5 128
O22- peroxide 1.0 149
 Name Bond Order Bond Length (pm)

O2+ oxonium ion 2.5 112.3

O2 dioxygen 2.0 120.07
O2- superoxide 1.5 128
O22- peroxide 1.0 149
He2 = 1s21s*2 B.O. = 0.5 (2-2) = 0  not exist

He2+ = 1s21s*1 B.O. = 0.5 (2-1) = 0.5  not real

chemical but spectroscopically existence
ii) O2, F2 & Ne2
O = 1S22s22p4  B.O. = 2; paramagnetic 
mystery for life (not in VBT)
Bond Lengths & Ionization E
bond order = 0.5 (Nb – Na)
Nb = # of bonding e; Na = # of antibonding e

i) O2
O2 = KK2s22s*22p2 π2p4π 2p*2
B.O. = 0.5 (8-4) = 2 O = O : 121 pm

ii) O22-
O2 = KK2s22s*22p2 π2p4π 2p*4
B.O. = 0.5 (8-6) = 1 O - O : 149 pm

iii) O2+
O2 = KK2s22s*22p2 π2p4π 2p*1
B.O. = 0.5 (8-3) = 2.5 O = O : 112 pm
iv) NO
NO = KK2s22s*22p2 π2p4π 2p*1
B.O. = 0.5 (8-3) = 2.5 N ≡ O : 115 pm
NO  NO+ + e I. E. = 894 kJ/mol
nitrosyl ion : NO+HSO4-; NO+BF4-

v) N2
N2 = KK2s22s*22p2 π2p4π 2p*
B.O. = 0.5 (8-2) = 3 N ≡ N : 106 pm
N 2  N 2+ + e I. E. = 1503 kJ/mol
Bond Length 비교
bonding antibonding
orbital orbital

increasing
nuclear charge
17.5 Photoelectron Spectroscopy
Photoelectron Spectroscopy(PES)
and Binding Energies

원자나 분자 내의 전자는 양자화된 에너지 준위(orbitals) 안에 존재

H2 + hv (photon)  H2+ + e-
I. E. = hv(photon) – K. E. of e-  결합E

원자나 분자로부터 전자를 떼어내기 위해 필요한 최소한의 에너지 → 이온

화 에너지, 떼어내려고 하는 전자가 위치하는 오비탈에 따라 다름.

PES : 다양한 원자나 분자에 특정한  의 빛을 쪼임.

(λ : vacuum ultraviolet(VUV)  UPS
X – ray  XPS or ESCA)

Electron Spectroscopy for Chemical Analysis

17.5 Photoelectron Spectroscopy
PES (UPS, XPS)

PES : 고E 빛 (UV, X-ray)  시료  광전자 방출 (eg, He(I) – 21.22eV)

BE = hν – ½ mev2

PES spectra of H2 & HCl

Photoelectron Spectroscopy

interact with
vibrational level
 strongly involved
in bonding
Correlation Diagram
(via Symmetry)

(2px, 2py)

(2pz)

Ex) He Ex) H2
Heteronuclear Diatomic Molecules

Polar bonding Ionic bonding

increasing Effective Nuclear Charge
gives more negative potential
 Heteronuclear diatomic molecules

*2s
2sA

2sB

2s

2s 2sA보다 2sB 를 닮았음

*2s 2sB 〃 2sA 〃 〃.
혹은, 2s = CA2sA + CB2sB , CA,CB > 0 ,
C B > CA
*2s = C′A2sA - C′B2sB
C′A > C′B
 Heteronuclear diatomic molecules

총 10개의 전자
(1sF)2(2sF)2 2 (2pxF)2(2pyF)2
비결합 오비탈

결합 오비탈 안에 두 개의 전자 → b.o. = 1

또한,  오비탈은 1s(H) 보다 2pz(F)를 더

닮았다. 즉 계수C가 더 크다 →
안의 전자는 F 에 보다 더 가까이 위치 : ionic
character
+ -
∴ H -F : 전기 음성도 차이에서 알고
있던 대로 쌍극자 모멘트
 Heteronuclear diatomic molecules

동종 이원자의 경우, CA = CB , etc.

이것만 제외하면, 나머지 상황은 동종 이원자의
경우와 동일함 eg) BO
 partial
secondary mixing C의 l.p.e (HOMO)
(more p-character)
Mt.에 donation 가능

mismatch

Huge
energy gap
O의 l.p.e
(more s-character) mismatch

lower
energy
∵ O has large E.N.C
& penetration
There is one σ-bonding from linear combination between hybrid orbital 2
(higher E) of oxygen atom and hybrid orbital 1 (lower E) of carbon atom!
Also, there are two π-bondings between px, py orbitals!
 Ionic Compounds

π-nonbonding (l.p.e)
∵ Symmetry mismatch

σ-bonding ?
But, similar to F Big E gap
σ-nonbonding (l.p.e)  Ion bonding!
∵ E mismatch

Very low E
due to big E.N.C.
 Heteronuclear diatomic molecules

eq) NaF의 오비탈 에너지를 보면.

3s(Na) - 2pz(F) →  오비탈
3s(Na) 이 매우 높음
3s(Na) *

2pz(F)
∴  는 2pz(F) 에 매우 유사함 
혹은,  = CA3s(Na) - CB2pz(F)
CA ~ 0 , C B ~ 1
∴ 안의 전자는 대부분 2pz(F)에 위치
 Na+ F- 의 상황(이온 결합)
MOs of Polyatomic Compounds
 Three Atomic Molecules

(eq) BeH2, VSEPR에 의하면 선형구조

z
HA Be HB

MO를 어떻게 만들까 ? 두 가지 방법

1) LCAO between M (center atom) and LGO (ligand group orbitals)
HA, HB : 1s AO
Be : 2s, 2pz AOs ( 2px ,2py 는 수소의 1s 와 상호작용
하지 않는다. 즉, overlap=0)
2) Hybridization of M and L AOs
 Polyatomic Molecules의 MO를 구하는 한 가지 방법

1. Determine the point group. 그리고 무한대 회전축을

가지는 경우는 가장 간단한 축으로 가정
eg) D∞h  D2h, C∞v  C2v
2. 주축은 z축으로
(비선형인 경우 바깥원자에서 중심원자로 향해 y축)
3. 리간드의 2s, 2p orbitals의 representation 구하기
4. 가약표현을 다시 기약표현으로 줄이고 그것에 맞는
ligand group orbitals (LGO)구하기  symmetry-adapted
linear combination (SALC)
5. 대칭과 Energy가 비슷한 중심원자와 LGO matching
6. 전체 MO의 수 = 전체 AO의 수
 FHF-
D∞h  D2h
 Group Orbitals of Fluoride Atoms
Symmetry Adapted Linear Combination (SALC)
= Terminal Atom Symmetrized Orbital (TASO)

From Character Table

 Symmetry mismatch
No overlap (non-bonding)
-13.6 eV

B3g B2u
B2g
-18.7 eV
B3u
Ag B1u

Covalent bond character

Too large energy gap (~30 eV)
No overlap (non-bonding)
Ag B1u
-40.2 eV
Ionic bond character
CO2  D∞h  D2h

From Character Table

B1u
Ag
Ag

B1u
π bonding Nonbonding
LUMO
Nonbonding (p-character)
HOMO (4개의 l.p.e.)

π bonding

σ bonding

Nonbonding (s-character)
(4개의 l.p.e.)
MOs of H2O

A.O. of O

SALC of H

by decomposition formula
 Nonbonding

~20 eV

Almost nonbonding
MOs of NH3

A.O. of N

SALC of H
Almost
nonbonding

2pz

2s
 Projection Operators
• The projection operator method is used to generated symmetry adapted linear
combinations in a basis.

<Procedure>
1. Choose Basis set.
2. Generate Reducible Representation.
3. Reduce to get Irred. Rep.
4. Use Projection Operator to create new basis set which
transforms as each of the Irrer. Rep.

Projection operators for Irred. Rep. Γa

P(Γa) = (l/h) Σ χi(Γa)Ri

where, l = Dimension of Irr. Rep. Γa

h = Order of Group
χi(Γa) = Character of Irr. Rep. Γa under Symm. oper. class i
Ri = Symm. Operator for class i (class 로 분리하지 않고 각각 적용)
 Projection Operator Method
for Finding M.O. for Irr. Rep.
P(Γa) = (l/h) Σ χi(Γa)Ri

1. Take any atomic orbital or set of orbitals.

2. Perform each Symm. Operation on it.

(Class must be divided into each Symm. Operation)

3. Multiply by the χ of the Irr. Rep. in question for each Symm. Operation.

4. Sum all the “Projections” made in step 3.

 Group Orbitals for σ-M.O. <SALC, TASO>
by Projection Operator (P(Γa) = (l/h) Σ χi(Γa)Ri)
1) P(A1)σ1 =1/6 { (1)Eσ1 + (1)C3σ1 + (1)C32σ1 + (1)σvσ1+ (1)σv’σ1 +
(1)σv”σ1 }
= 1/6 { 2σ1 + 2σ2 + 2σ3 }
∴ψσ(A1’) = (1/√3) ( σ1 + σ2 + σ3 )
2) P(A1’)σ2 = (1/3) ( σ1 + σ2 + σ3 ) Unique M.O.
3) P(A1’)σ3 = (1/3) ( σ1 + σ2 + σ3 ) same as P(A1’)σ1
4) P(E’)σ1 = 2/6 { (2)Eσ1 + (-1)C3σ1 + (-1)C32σ1 + 0 + 0 + 0 }
= 1/3( 2σ1 - σ2 - σ3 )
= 1/3 ( 2σ1 - σ2 - σ3 )
∴ψσ(E’)a = (1/√6) ( 2σ1 - σ2 - σ3 )
5) P(E’)σ2 = (1/3) ( 2σ2 - σ3 - σ1 )
6) P(E’)σ3 = (1/3) ( 2σ3 - σ1 - σ2 ) Unique M.O.
= by C31
Just difference of rotation
= by C32
But, E’ is a 2-dimensional representation.
ie, two M.O. is expected!!
Thus, to find the other unique M.O.,
we substract the M.O. created by just rotation!!
C31 Rot; 5) P(E’)σ2 = (1/3) ( 2σ2 - σ3 - σ1 )
- ) C32 Rot; 6) P(E’)σ3 = (1/3) ( 2σ3 - σ1 - σ2 )
= σ2 - σ3
∴ψσ(E’)b = (1/√2) ( σ2 - σ3 ) Another unique M.O.

Total Group Orbitals for σ-bonding;

H H

+ 2+

+ + - - - +
H H H H
Boron Trifluoride – Group Theoritical Treatment I

B atom: 2s  A1’
2pz  A2”
2px, 2py  E’
D3h E 2C3 3C2 σh 2S3 3σv
ГF2s 3 0 1 3 0 1

A1’ = 1/12{(1)(1)(3)+(2)(1)(0)+(3)(1)(1)+
(1)(1)(3)+(2)(1)(0)+(3)(1)(1)} = 1
A2’ = 1/12{3+0-3+3+0-3} = 0
E’ = 1/12{6-0-0+6-0-0} = 1
A1” = 1/12{3+0+3-3-0-3} = 0
A2” = 1/12{3+0-3-3-0+3} = 0
E” = 1/12{6-0-0-6+0+0} = 0
∴ ГF2s = A1’ + E’
D3h E 2C3 3C2 σh 2S3 3σv
ГF2pz 3 0 -1 -3 0 1

A1’ = 1/12{(1)(1)(3)+(2)(1)(0)+(3)(1)(-1)+
(1)(1)(-3)+(2)(1)(0)+(3)(1)(1)} = 0
A2’ = 1/12{3+0+3-3+0-3} = 0
E’ = 1/12{6-0-0-6-0+0} = 0
A1” = 1/12{3+0-3+3-0-3} = 0
A2” = 1/12{3+0+3+3-0+3} = 1
E” = 1/12{6-0-0+6+0+0} = 1
∴ ГF2pz = A2” + E”
 D3h E 2C3 3C2 σh 2S3 3σv
ГF2px,2py 6 0 0 6 0 0

A1’ = 1/12{(1)(1)(6)+(2)(1)(0)+(3)(1)(0)+
(1)(1)(6)+(2)(1)(0)+(3)(1)(0)} = 1
A2’ = 1/12{6+0-0+6+0-0} = 1
E’ = 1/12{12-0+0+12+0+0} = 2
A1” = 1/12{6+0+0-6-0-0} = 0
A2” = 1/12{6+0-0-6-0+0} = 0
E” = 1/12{12-0+0-12+0+0} = 0
∴ ГF2px,py = A1’ + A2’ + 2E’
 MOs of BF3

D3h

B atom: 2s  A1’
2pz  A2”
2px, 2py  E’

F atom:
2s = A1’ + E’
2pz = A2” + E”
2px, py= A1’ + A2’ + 2E’
Boron Trifluoride – Group Theoretical Treatment II

BF3  by VBT
sp2 hybridized
Trigonal Planar structure

 D3h point group

A.O. of B
 σ-Bonding

Basis set  Bond Vector

E 2C3 3C2 σh 2S3 3σv

Γσ 3 0 1 3 0 1

by Decomposition Formula
aA1’ = (1/12) { 1x1x3 + 0 + 3x1x1 + 1x1x3 + 0 + 3x1x1 } = 1
aA2’ = (1/12) { 1x1x3 + 0 + 3x(-1)x1 + 1x1x3 + 0 + 3x(-1)x1 } = 0
aE’ = (1/12) { 1x2x3 + 0 + 3x0x1 + 2x1x3 + 0 + 0 } = 1
aA1” = 0, aA2” = 0, aE” = 0

∴ Γσ = A1’ + E’ ↔ A1’ for s orbital of B

E’ for px, py orbital of B
 Group Orbitals for σ-M.O. <SALC, TASO>
by Projection Operator (P(Γa) = (l/h) Σ χi(Γa)Ri)
1) P(A1’)σ1 =1/12 { (1)Eσ1 + (1)C3σ1 + (1)C32σ1 + (1)(C2)1σ1 + (1)(C2)2σ1
+ (1)(C2)3σ1 + (1)σhσ1 + (1)S3σ1 + (1)S32σ1 + (1)σvσ1
+ (1)σv’σ1 + (1)σv”σ1 }
= 1/12 { 4σ1 + 4σ2 + 4σ3 }
∴ψσ(A1’) = (1/√3) ( σ1 + σ2 + σ3 ) Unique M.O.
2) P(A1’)σ2 = (1/√3) ( σ1 + σ2 + σ3 )
same as P(A1’)σ1
3) P(A1’)σ3 = (1/√3) ( σ1 + σ2 + σ3 )
4) P(E’)σ1 = 2/12 { (2)Eσ1 + (-1)C3σ1 + (-1)C32σ1 + 0 + 0 + 0 + (2)σhσ1
+ (-1)S3σ1 + (-1)S32σ1 + 0 + 0 + 0 }
= 2/12( 2σ1 - σ2 - σ3 + 2σ1 - σ2 - σ3 )
= 2/12 ( 2σ1 - σ2 - σ3 )
∴ψσ(E’)a = (1/√6) ( 2σ1 - σ2 - σ3 ) Unique M.O.
5) P(E’)σ2 = (1/√6) ( 2σ2 - σ3 - σ1 ) = by C31
Just difference of rotation
6) P(E’)σ3 = (1/√6) ( 2σ3 - σ1 - σ2 ) = by C32
But, E’ is a 2-dimensional representation.
ie, two M.O. is expected!!
Thus, to find the other unique M.O.,
we substract the M.O. created by just rotation!!
C31 Rot; 5) P(E’)σ2 = (1/√6) ( 2σ2 - σ3 - σ1 )
- ) C32 Rot; 6) P(E’)σ3 = (1/√6) ( 2σ3 - σ1 - σ2 )
= 3σ2 - 3σ3
∴ψσ(E’)b = (1/√2) ( σ2 - σ3 ) Another unique M.O.

Total Group Orbitals for σ-bonding;

+ 2+

+ + - - - +
 π-Bonding

Basis set  π-bonding between pz orbital of F

E 2C3 3C2 σh 2S3 3σv

Γπ 3 0 -1 -3 0 1

by Decomposition Formula
∴ Γπ = A2” + E” ↔ A2” for pz orbital of B
(from Character Table)

∴ π-bonding  between A2”(F) & A2”(B)

Nonbonding  E”
 Group Orbital for π-Bonding
P(A2”)π1 = 1/12 { (1)Eπ1 + (1)C3π1 + (1)C32π1 + (-1)(C2)1π1 + (-1)(C2)2π1
+ (-1)(C2)3π1 + (-1)σhπ1 + (-1)S3π1 + (-1)S32π1 + (1)σvπ1
+ (1)σv’π1 + (1)σv”π1 }
= 1/12 { 4π1 + 4π2 + 4π3 }
∴ψa2”(π) = (1/√3) ( π1 + π2 + π3 )
P(A2”)πBoron  Do not need due to only one π-bonding possible
through pz of Boron.
 Total M.O. of BF3

4 bonding orbitals (3 σ-bond & 1 π-bond)

4 antibonding orbitals correspond to 4 bonding orbital
2 nonbonding orbitals from e”(pz)
3 nonbonding orbitals from 3 2s of F (too low energy)
3 nonbonding orbitals from 3 2py of F (poor orientation)

Total number of M.O. = 16 !!!

x
z

y
Home Work

NH3에 대해서 BF3에서와 마찬가지로

아래의 두 가지의 Group Theoretical 방법을 이용해서
MO를 완성하시오.

1) Pictorial Method

2) Projection Operator
 Hybridization

Lewis 모델(localized e pair/bond, symmetry) & VSEPR →

분자의 3차원 구조.
오비탈 혼성의 개념은 위의 구조를 양자역학을 사용해서 설
명하기 위한 아이디어이다.

∴ 분자의 구조를 이해하기 위한 도구로 사용하되,

너무 심각하게 받아들이지는 말 것.
만일 혼성의 결과가 정확한 결과(실험 혹은 이론)와 다르
다면 혼성화를 포기해야 한다. 데이터가 잘못된 것이 아니다.
 Hybridization
The problem of accounting for the true geometry of molecules and the
directionality of orbitals is handled using the concept of hybrid orbitals.
Hybrid orbitals are mixtures of atomic orbitals and are treated mathematically
as Linear Combinations of the appropriate s, p and d Atomic Orbitals (LCAO).

Linear sp hybrid orbitals

A 2s orbital superimposed
on a 2px orbital The two resultant sp
hybrid orbitals that are
directed along the X-axis
(in this case)

The 1/2 are normalization coefficients.

 Orthogonality and Normalization
Two properties of acceptable orbitals (wavefunctions) that we have not yet
considered are that they must be orthogonal to every other orbital and they
must be normalized. These conditions are related to the probability of finding
an electron in a given space.
Orthogonal means that the integral of the product of an orbital with any other
orbital is equal to 0, i.e.:

where n  m and t means that the integral

is taken over “all of space” (everywhere).

Normal means that the integral of the product of an orbital with itself is equal
to 1, i.e.:

This means that we must find normalization coefficients that satisfy

these conditions. Note that the atomic orbitals () we use can be
considered to be both orthogonal and normal or “orthonormal”.
 Example of the orthogonality of 1 and 2

Thus our hybrid sp orbitals are orthogonal to each other, as required.

 Hybridization
Valence bond theory treatment of a linear molecule: the bonding in BeH2
BeH2 The promotion energy can
2s 2p be considered a part of the
Be energy required to form
hybrid orbitals.
Be*
sp 2p
Be* (sp)

2H
1s 1s

The overlap of the hybrid orbitals on Be with the 1s orbitals on the H

atoms gives two Be-H (sp)-1s  bonds oriented 180° from each other.
This agrees with the VSEPR theory prediction.
Valence bond theory treatment of a trigonal planar molecule: the bonding in BH3

2s 2p
B

B*

sp2 2p
B* (sp2)

This gives three sp2 orbitals

that are oriented 120° apart
in the xy plane – be careful:
the choice of axes in this
example determines the set
of coefficients.
 The coefficients in front of each atomic wavefunction indicate the amount
of each atomic orbital that is used in the hybrid orbital. The sign indicates
the orientation (direction) of the atomic orbitals. Remember that you have
to use each atomic orbital completely (columns) and that each hybrid
must be normal (rows). Check this by summing the squares of the
coefficients.
The signs in front
1/3 + 1/6 + 1/2 = 1 of the coefficients
So this hybrid is normal indicate the
direction of the
hybrid:
1/3 + 1/6 + 1/2 = 1 1: -x, +y
So this hybrid is normal
2: -x, -y
3: +x, 0y
1/3 + 4/6 = 1
So this hybrid is normal y

1/3 + 1/3 + 1/3 = 1 1/6 + 1/6 + 4/6 = 1 1/2 + 1/2 = 1

x
So the entire s orbital So the entire px orbital So the entire py orbital
has been used has been used has been used
Valence bond theory treatment of a trigonal planar molecule: the bonding in BH3

sp2 2p
B*

3H
1s 1s 1s

The overlap of the sp2 hybrid orbitals on B with the 1s orbitals on the H
atoms gives three B-H (sp2)-1s  bonds oriented 120° from each other.
This agrees with the VSEPR theory prediction.
Valence bond theory treatment of a tetrahedral molecule: the bonding in CH4

2s 2p
C

C*
sp3
C* (sp3)

This gives four sp3 orbitals

that are oriented in a
tetrahedral fashion.
Valence bond theory treatment of a tetrahedral molecule: the bonding in CH4

2s 2p
C

C*
sp3
C* (sp3)

4H
1s 1s 1s 1s

The overlap of the sp3 hybrid orbitals on C with the 1s orbitals on the H
atoms gives four C-H (sp3)-1s  bonds oriented 109.47° from each other.
This provides the tetrahedral geometry predicted by VSEPR theory.
 Valence bond theory treatment of a trigonal bipyramidal molecule:
the bonding in PF5
3s 3p PF5 has an VSEPR theory
P AX5 geometry so we need
3d hybrid orbitals suitable for
P* bonds to 5 atoms. ns and np
combinations can only
P* (sp3d) 3d provide four, so we need to
use nd orbitals (if they are
available).

3s 3pz 3py 3px 3dz2

sp3dz2

The appropriate mixture to form a trigonal bipyramidal arrangement

of hybrids involves all the ns and np orbitals as well as the ndz2
orbital.
 Valence bond theory treatment of a trigonal bipyramidal molecule
The orbitals are treated in two different sets.

These coefficients are

exactly the same as the
result for the trigonal
planar molecules
because they are
derived from the same
orbitals (sp2)

These coefficients are

similar to those for the sp
hybrids because they are
formed from a combination
of two orbitals (pd).

Remember that d orbitals are more diffuse than s or p orbitals so VBT

predicts that the bonds formed by hybrids involving d orbitals will be
longer than those formed by s and p hybrids.
 Valence bond theory treatment of a trigonal bipyramidal molecule:
the bonding in PF5

P* (sp3d) 3d

F
2s 2p
F F
2s 2p 2s 2p
F
2s 2p
F
2s 2p
The overlap of the sp3d hybrid orbitals on P with the 2p orbitals on the F
atoms gives five P-F (sp3d)-2p  bonds in two sets: the two axial bonds
along the z-axis (180° from each other) and three equatorial bonds in
the xy plane (120° from each other and 90° from each axial bond). This
means that the 5 bonds are not equivalent!
 The square pyramidal AX5 geometry requires mixing with a different
d orbital than in the trigonal bipyramidal case.

Sb(C6H5)5

d orbitals

You should consider what orbital(s) would be useful for such a geometry
and we will see a way to figure it out unambiguously when we examine the
symmetry of molecules.
 Valence bond theory treatment of an octahedral molecule:
the bonding in SF6
3s 3p
S
3d
S*

S* (sp3d2) 3d

F F F F F F

3s 3pz 3py 3px 3dz2 3dx2-y2 sp3d2

The overlap of the sp3d2 hybrid orbitals on S with the 2p orbitals on the F
atoms gives six S-F (sp3d2)-2p  bonds 90° from each other that are
equivalent. You can figure out the normalization coefficients.
 Valence bond theory treatment of p-bonding: the bonding in ClNO
2s 2p
N
sp2 2p There are three “objects” around N so the
N*(sp2) geometry is trigonal planar. The shape is
given by AX2E (angular or bent).
  p

Cl O
3s 3p 2s 2p

A drawing of the VBT p bond

in ClNO.

The overlap of the sp2 hybrid orbitals on N with the 3p orbital on Cl and
the 2p orbital on O give the two  bonds and it is the overlap of the “left
over” p orbital on N with the appropriate orbital on O that forms the (2p-
2p) p bond between the two atoms.
 Valence bond theory treatment of p-bonding: the bonding in the nitrate anion
2s 2p
N

N+
sp2 2p
N+*(sp2) There are three “objects” around N so the
geometry is trigonal planar. The shape is

given by AX3 (trigonal planar).
O-  p

2s 2p
O-
2s 2p
O VBT gives only one of the
canonical structures at a time.
2s 2p
The overlap of the sp2 hybrid orbitals on N with the the 2p orbitals on the
O give the three (sp2-2p)  bonds and it is the overlap of the “left over” p
orbital on N with the appropriate orbital on the uncharged O atom that
forms the (2p-2p) p bond.
 Valence bond theory treatment of p-bonding: the bonding in ethene
2s 2p
Each C

Each C*
There are three “objects”
sp2 2p
around each C so the
C*(sp2) p geometry is trigonal planar at
sp2 2p each carbon. The shape is

  given by AX3 for each carbon.
  C*(sp2)
4H
1s 1s 1s 1s

The overlap of the sp2 hybrid orbitals on C with the the 1s orbitals on
each H give the four terminal (sp2-1s)  bonds. The double bond
between the C atoms is formed by a (sp2- sp2)  bond and the (2p-2p)
p bond.
 Valence bond theory treatment of p-bonding: the bonding in SOCl2

3s 3p
S
3d
S*
sp3 3d There are four “objects”
S*(sp3) around S so the geometry is
tetrahedral and the shape is
  p
 given by AX3E (pyramidal).
Cl Cl O
2s 2p

The overlap of the sp3 hybrid orbitals on S with the 3p orbitals on Cl and
the 2p orbital on O give the three  bonds and, because the lone pair is
located in the final sp3 hybrid, it is the overlap of the “left over” d orbital
on S with an appropriate p orbital on O that forms the (3d-2p) p bond in
the molecule.
 Valence bond theory treatment of bonding: a hypervalent molecule, ClF3
3s 3p
Cl
3d
Cl*
There are five “objects” around
Cl* (sp3d) 3d
Cl so the geometry is trigonal
bipyramidal and the shape is
F F F given by AX3E2 (T-shaped).
Consider this: Why are such
molecules T-shaped instead of
pyramidal?

The overlap of the sp3d hybrid orbitals on Cl with the 2p orbitals on the F
atoms gives three P-F (sp3d)-2p  bonds in two sets: the two axial bonds
along the z-axis (less than 180° from each other because of the
repulsion from the lone pairs) and the one equatorial bond halfway
between the other Cl bonds. Again, the bond lengths will not be the
same because there is more d contribution to the axial hybrid orbitals.