BONDING THEORIES
MO diagrams can be adjusted to the varying degree of covalency between the
ligands and the metal, from nearly ionic to polar covalent
VALENCE BOND THEORY
VALENCE BOND THEORY
formation of molecules occurs by bringing together complete
atoms,
which essentially retain their original character such that atomic
orbitals are not significantly altered in the molecule
the overlap of two atomic orbitals forms one bond
localized bond – 100% likelihood the paired electrons will be
located between the nucleus
VBT
fails
to
account
for
excited
states
and
magne5c
proper5es
MOLECULAR ORBITAL THEORY
The nuclei of the individual atoms in the molecule are treated
as if they formed a polycentric nucleus embedded in an
electron distribution that surrounds the entire molecule
the overlap of two atomic orbitals forms two molecular
orbitals
delocalized bonding MO – less than 100% likelihood the
electrons will be located between the nucleus, although the
region of electron density probability lies along the bond axis
delocalized antibonding MO – a node indicates that electron
density is increased in regions away from the bond axis
MOLECULAR ORBITAL THEORY: the LCAO method
BONDING MODELS
H2+ H (1s1) + H+ (1s)
VBT
1s
+
1s
→
.
.
σ1s
=
φA(1)φB(2)
+
φA(2)φB(1)
MOT
.
.
σ*u1s
=
φA1s
–
φB1s
1s
+
1s
.
.
σg1s
=
φA1s
+
φB1s
PROBABILITY DENSITIES OF MOLECULAR ORBITALS
the Slater overlap integral S = ∫φAφBdτ defines the nature and
efficiency of the interaction of orbitals
calculation of S becomes increasingly difficult as the number of
electrons increase, but a qualitative picture is often sufficient
S>0 enhanced electron density between nuclei
S<0 reduced electron density between nuclei
S=0 no change in electron density between nuclei
BONDING MOLECULAR ORBITALS
S>0
enhanced electron density between nuclei
nuclei are shielded from each other by the intervening
electrons, thus attraction between the nuclei and electrons is
enhanced
positive overlap of atomic orbitals
the energy of the molecule is lowered compared to the atoms
ANTIBONDING MOLECULAR ORBITALS
S<0
reduced electron density between nuclei
nuclei are partially bared to each other, and the electrons tend
to be in regions where mutual attraction by both nuclei is
severely reduced
negative overlap of atomic orbitals
the energy of the molecule is raised compared to the atoms
NONBONDING MOLECULAR ORBITALS
S=0
no change in electron density between nuclei
the distribution of electron density is essentially the same as
that described by atomic orbitals
all interacting regions of the same wave function sign have
opposing interactions, thus the electron distribution is
unchanged
the energy of the molecule is unchanged compared to the atoms
NONBONDING MOLECULAR ORBITALS
S=0
all interacting regions of the same wave function sign have
opposing interactions, thus the electron distribution is unchanged
ORBITAL OVERLAP
TYPES OF ORBITAL OVERLAP
SIGMA OVERLAP
the difference between σ and π interactions can be described
in terms of symmetry with respect to the internuclear axis
σ overlap reinforcement of electron density along the
internuclear axis (by convention the z-axis)
the amplitude is symmetrically distributed around the bond axis
overlap of s and pz orbitals
cylindrical electron density
SIGMA OVERLAP
σ overlap bonding and antibonding interactions can be obtained
from the overlap of s and pz orbitals
s
±
s
s
±
pz
.
.
σ*u1s
1s
+
1s
.
.
σg1s
SIGMA OVERLAP
σ overlap bonding and antibonding interactions can be obtained
from the overlap of pz orbitals
pz
±
pz
PI OVERLAP
the difference between σ and π interactions can be described
in terms of symmetry with respect to the internuclear axis
π overlap equal reinforcement above and below the internuclear
axis with opposite signs across this axis and a nodal
surface along the bond axis
antisymmetric with respect to the internuclear axis
overlap of px or py orbitals
PI OVERLAP
π overlap overlap of px or py orbitals
PI OVERLAP
π overlap overlap of px or py orbitals
ORBITAL OVERLAP WITH d ORBITALS
bonding antibonding non-bonding
σ (dx2-‐y2
+
pz)
σ*(dx2-‐y2
–
pz)
dxz
+
s
π (dxz+
px)
π* (dxz
–
px)
π (dxz+
dxz)
π* (dxz
–
dxz)
DELTA OVERLAP
metal-metal bonding can involve a third type of orbital
δ overlap interaction of all four lobes of pairs of dx2-y2 or dxy
orbitals
symmetric at 180° but
antisymmetric at 90° with respect
to the internuclear axis
EFFICIENCY OF ORBITAL OVERLAP
MOs arise from interactions between AOs that:
(i) have the same symmetry with respect to the internuclear axis
(ii) overlap significantly
(iii) have similar energy
1s ± 1s → σg1s + σ*u1s
2s ± 2s → σg2s + σ*u2s
1s ± 2s → insignificant overlap
BONDING MOs
constructive overlap of two atomic orbitals leads to accumulation
of electron density in the region of the two nuclei – bonding MO
interac.ng
system
ψ+
=
φA
+
φB
ψ+2
=
(φA
+
φB)2
=
φA2
+
2φAφB
+
φB2
φA
φB
non-‐interac.ng
system
ψ2 = (φA) 2
+
(φB) 2
ANTIBONDING MOs
deconstructive overlap of two atomic orbitals leads to reduced
electron density in the region of the two nuclei – antibonding MO
interacting system
ψ- = φA – φB
ψ-2 = (φA – φB)2
= φA2 – 2φAφB + φB2
φA
φB
non-interacting system
ψ2 = φA2 + φB2
MO ENERGY LEVEL DIAGRAM FOR H2+
qualitative picture of molecular orbital energy
an.bonding
MO
bonding
MO
ΔEdiss
=
–ΔE
=
255
kJ/mol
(2.6
eV)
