MO ENERGY LEVEL DIAGRAM FOR H2+

ψ-
σ *
u1s

E φA, φB 1s 1s

–ΔE
ψ+
σg1s

1s1 H H2+ H+

electron configuration = (σg1s)1 bond order = ½

bond order = 1/2(electrons in bonding MOs – electrons in antibonding Mos)

ΔEdiss  =    255  kJ/mol    =  –½ΔE    bond  length  =  1.06  Å  
ENERGY LEVEL DIAGRAM FOR H2

ψ-
σ *u1s
E φA, φB 1s 1s

–ΔE
ψ+
σg1s

1s1 H H2 H 1s1

electron configuration = (σg1s)2 bond order = 1

ΔEdiss = 436 kJ/mol = –ΔE bond length = 0.74 Å

ENERGY LEVEL DIAGRAM FOR He2+

ψ-

σ*u1s   +ΔE  

E   φA,  φB   1s     1s  

–ΔE  
ψ+

σg1s  

 1s2              He                          He2+                            He+        1s1  

electron  configura@on  =  (σg1s)2(σ*u1s)1                    bond  order  =  ½  

ΔEdiss  =    251  kJ/mol  =  (–ΔE  +  ½ΔE)                        bond  length  =  1.08  Å  

ENERGY LEVEL DIAGRAM FOR He2

ψ-

σ*u1s   +ΔE  

E   φA,  φB   1s     1s  

–ΔE  
ψ+

σg1s  

1s2              He                          He2                              He        1s2  

electron  configura@on  =  (σg1s)2(σ*u1s)2                    bond  order  =  0

ΔEdiss  ~  0  kJ/mol  =  (–ΔE  +  ΔE)                          bond  length  =  large  

MOLECULAR ORBITAL GENERALIZATIONS

1.  bonding  MOs  always  lie  lower  in  energy  than  an@bonding  

 MOs  formed  from  the  same  AOs  

2.  nonbonding  MOs  tend  to  have  energies  between  those  of    

 bonding  and  an@bonding  MOs  formed  from  similar  AOs  

3.  π  interac@ons  tend  to  have  less  effec@ve  overlap  than  σ    

 interac@ons,  thus  π-­‐bonding  MOs  tend  to  have  higher  energies  
 than  σ-­‐bonding  MOs  and  π*-­‐an@bonding  MOs  tend  to  have  
 lower  energies  than  σ*-­‐an@bonding  MOs  formed  from    
 similar  AOs  

4.    MO  energies  tend  to  rise  as  the  number  of  nodes  increase  
MO DIAGRAM FOR 2nd ROW HOMONUCLEAR DIATOMICS
σ *u2pz  

π*g2px  π*g2py  

2p     πu2px  πu2py   2p  

E   σg2pz  

σ *u2s  

2s     2s  

σg2s  
X                                                      X2                                                      X  
ENERGY LEVEL DIAGRAM FOR O2
σ *u2pz  
π*g2px  π*g2py  

2p     πu2px  πu2py   2p  

E   σg2pz  

σ*u2s  

2s     2s  

σg2s  
O                                                      O2                                                      O  
ENERGY LEVEL DIAGRAM FOR HOMONUCLEAR DIATOMICS
Z = 8–10
ENERGY LEVEL DIAGRAM FOR B2
Experimental  evidence  indicates  
σ *u2pz   that  B2  has  2  unpaired  electrons!  

π*g2px  π*g2py  

2p     πu2px  πu2py   2p  

E  
σg2pz  

σ *u2s  
2s     2s  

σg2s  
B                                                      B2                                                      B  
2s AND 2p ATOMIC ORBITAL ENERGY
ENERGY LEVEL DIAGRAM FOR HOMONUCLEAR DIATOMICS
Z = 5–7
ENERGY LEVEL DIAGRAM FOR HOMONUCLEAR DIATOMICS
Z = 5–7
ENERGY LEVEL DIAGRAM FOR N2
ENERGY LEVEL DIAGRAM FOR HOMONUCLEAR DIATOMICS
Z  =  5–7                  Z  =  8–10  
ENERGY LEVEL DIAGRAM FOR HOMONUCLEAR DIATOMICS
BONDING PARAMETERS FOR HOMONUCLEAR DIATOMICS

   valence  electrons  bond  bond    bond    magn.  

 #  configura@on  order  length  strength  
         (pm)  (kJ/mol)  

H2    2  1σg2  1    74  431  dia  

He2    4  1σg22σu2    0  −  −  −  
Li2    2  1σg22σu23σg2    1  267  105  dia  
Be2    4  1σg22σu23σg24σu2  0  −  −  −  
B2    6  1σg22σu23σg24σu21πu2  1  159  289  para  
C2    8  1σg22σu23σg24σu21πu4  2  124  599  dia  
N2    10  1σg22σu23σg24σu21πu45σg2  3  110  942  dia  
O2    12  1σg22σu23σg24σu25σg21πu42πg2  2  121  494  para  
F2    14  1σg22σu  3σg24σu25σg21πu42πg4  1  141  154  dia  
Ne2    16  1σg22σu23σg24σu25σg21πu42πg46σu2  0    −  −    −  
ENERGY LEVEL DIAGRAM FOR HETERONUCLEAR DIATOMICS

ψ-
ψ-  =  a'φA  –  b'φB    
           a  ≠  b  
φX  
E  
ΔEN  
φY  

ψ+   ψ+  =  aφA  +  bφB  

X                                XY                                  Y  

bonding orbitals possess greater Y then X character;

s and p interactions can be more significant versus X2
ENERGY LEVEL DIAGRAM FOR HF
σ *   1σ22σ21π4    

1s  
πnb

2p  
E  

nonbonding   σ   greater  F  character  –    

polar  covalent  bond  

2s  
σnb  

H                              HF                                      F  
nonbonding  orbitals  no  interac@on  of  wave  func@ons  

100%  F  character  lone  pairs  on  F  (2px,  2py  and  2s  orbitals)  
ENERGY LEVEL DIAGRAM FOR HF

anAbonding  

ψ  =  aφH1s  +  bφF2s  +  cφF2pz  

nonbonding  
bonding  

nonbonding  
DEGREES OF COVALENCY
σ*u  

homonuclear  –  covalent   A   A  

ΔEN  =  0   ΔE  
       a  =  b   σg  

σ*u  
heteronuclear  –  polar  covalent   A  

ΔEN  =  small   B  
ΔE  
 a  <  b  for  σg  
σg  

heteronuclear  –  ionic   A  
σ*u  

ΔEN  =  large  
             a  ~  0,    b  ~  1  for  σg  
ΔE  
B  
σg  
BONDING AND ELECTRONEGATIVITY

large ⏐ΔEN⏐ ionic bond (>1.5)

small ⏐ΔEN⏐ polar covalent bond (<1.5)

zero ⏐ΔEN⏐ nonpolar covalent bond

NaCl ⏐ΔEN⏐ = ⏐1.0 – 3.0⏐ = 2.0

HCl ⏐ΔEN⏐ = ⏐2.1 – 3.0⏐ = 0.9

Cl2 ⏐ΔEN⏐ = 0
ENERGY LEVEL DIAGRAM FOR CO – 1

anAbonding  
anAbonding  (LUMO)  

largely  nonbonding  (HOMO)  

bonding  

bonding  

largely  nonbonding  
MOLECULAR ORBITALS OF CO – II
MOLECULAR ORBITALS OF CO – III

LUMO

LUMO

HOMO

HOMO
CARBON MONOXIDE AS A LIGAND

the frontier MOs have more carbon than oxygen character

the electron density of the HOMO is primarily on carbon, which is

able to form a σ bond with metal d orbitals

M + :C≡O → M – CO coordinate covalent bond

σ*  
3dx2-­‐y2  

CO  HOMO  

σ  

CO                      M-­‐CO                          M  
CARBON MONOXIDE AS A LIGAND

the frontier MOs have more carbon than oxygen character

the empty antibonding LUMOs are able to participate in π back-

bonding with a metal

π*  

CO  LUMO  

3dxz  

π  

CO                      M-­‐CO                          M  
CONSTRUCTION OF MOLECULAR ORBITAL DIAGRAMS

for simple molecules, the symmetries of orbitals of the central atom

are matched with those of mathematical combinations of orbitals on
the terminal atoms

the mathematical constructs of pendant atom atomic orbitals are called

symmetry-adapted linear combinations (SALCs) and generally do not
have physical meaning outside their use in constructing MOs

ψSALC  =  Σciφi  =  c1φ1  ±  c2φ2  ±  c3φ3  ±  …  ±  cnφn  

the resulting LCAO-MOs resemble those of diatomic molecules and

have the form

 ΨMO  =  aψAO(central  atom)  ±  bψSALC(all  pendant  species)