강의자료 저작권 관련 유의사항 안내

“본 강의자료는 연세대학교 학생들을 위해

수업목적으로 제작ㆍ게시된 것이므로 수업목적 외
용도로 사용할 수 없으며, 다른 사람들과 공유할 수
없습니다. 위반에 따른 법적 책임은 행위자 본인에게
있습니다.”

나. 금지되는 행위
(1) 위와 같이 내려 받은 강의자료를 수강생 본인 외 제3자에게 배포(출력물의 경우), 전송(파일
업로드)하는 행위
(2) 강의자료를 수강생 외에는 (i) 이용할 수 없도록 하는 접근제한조치, (ii) 복제할 수 없도록
하는 복제방지조치를 무력화하는 행위. 예컨대 강의자료가 게시된 와이섹 등에 접근할 수 있는
아이디와 비밀번호를 타인과 공유하거나 알려주는 행위, 강의자료에 부착된 복제방지조치를
무력화하는 해킹 행위 등
(3) 특히 동영상을 포함하여 강의자료를 인터넷에 게시 또는 타인에게 전송하는 순간, 외국의
저작권 침해가 될 수 있고, 심각한 소송의 대상이 될 수 있습니다. 해당 강의자료에 외국의
저작물이 포함되어 있을 수 있고, 그것이 외국에서 접근가능한 상태가 되기 때문입니다. 따라서,
강의자료를 타인과 공유하거나 전송 및 공개하는 행위를 하여서는 안 됩니다.
Materials Inorganic Chemistry

Chapter 5. Molecular Orbitals

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

/PESRSON/FIFTH EDITION/117p
 Formation of Molecular Orbitals from
Atomic Orbitals
- Molecular orbital (MO) theory presumes that atomic orbitals (AO) can be
mixed together to create MO.

Linear combination of atomic orbital (LCAO)

: The sums and differences of the atomic wave functions
- As the distance between two atoms is decreased, their orbitals overlap,
resulting in the formation of molecular orbital (MO).
- Electrons in bonding MO occupy the space between the nuclei. The
electrostatic forces between the electrons and the two positive nuclei holds
together.

Three conditions for overlap

1. Symmetry match of AO
2. Similar energy of AO
3. Short distance between the atoms
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/117p
Molecular Orbitals from s Orbitals
Bonding orbital (sign match of y1 and y2)
: Increased electron density between the nuclei and lower energy.
Antibonding orbital (sign mismatch of y1 and y2)
: Decreased electron density between the nuclei and higher energy.
Asterisk demotes the antibonding orbital.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/118p

If the two AO are identical, the coefficients are nearly identical.

Nonbonding orbital: The energy of a nonbonding orbital is essentially that
of an AO, because the orbital on one atom has a symmetry that does not
match any orbitals on the other atom.
Molecular Orbitals from p Orbitals
- pz orbitals: s and s* orbitals
- px, py orbitals: p and p* orbitals

- The overlap of two regions of

opposite sign leads to a node of zero
electron density.
- s + px orbitals: the bonding and
antibonding effects cancel and no
MO forms.
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/119p
 Molecular Orbitals from d Orbitals
Three types of bonding of d orbitals
1. dz2-dz2 interaction: s-type bonding, end-to-end overlap
2. dxz-dxz interaction: p-type bonding, side-to-side overlap
3. dxy-dxy interaction: d-type bonding, four-lobe overlap

- Order of relative energies

s < p < d < d* < p* < s*

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/122p
 Types of Molecular Orbitals
MO designation
1. s bonding: overlap of orbital
in one region of space
2. p bonding: overlap of orbital
in two regions of space
3. d orbital: overlap of orbital
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/120p

in four regions of space

Bond strength: s > p > d

Nonbonding Orbitals and Other Factors
- If there are three AOs with similar energy, three MOs form; bonding
MO, antibonding MO, and nonbonding MO with the original energy.

- The relative energies of AOs are very important in forming MOs.

- With two AOs with the same energies, the resulting interaction is strong.
- With two AOs with quite different energies, the interaction is weak.
- The resulting MOs have energies and shapes closer to the original AOs.
- The closer the energy match, the stronger the interaction.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/122p
 Homonuclear Diatomic Molecules
- Electrons fill the MO according to the same rules that govern the filing
of AO, aufbau principle, Hund’s rule, Pauli exclusion principle.

- The greater the bond order is,

the stronger the bond strength.

- The subscript g: gerade,

symmetric orbitals to inversion.
- The subscript u: ungerade,
antisymmetric orbitals to
inversion.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/123, 124p
 Orbital Mixing
- Orbitals with similar but not equal energies interact if they have
appropriate symmetries.
- When two MO of the same symmetry have similar energies, they interact
to lower the energy of the lower orbital and raise the energy of the higher
orbital.
- Mixing: the sg(2s) and sg(2p) orbitals can interact to lower the energy of
sg(2s) and to raise that of sg(2p) orbitals.

- For homonuclear diatomic molecules, c1 = c2 and c3 = c4 in each of MOs.

- The lowest energy MO has larger values of c1 and c2, the highest has
larger values of c3 and c4.
- After mixing, the symmetry of four MOs remain the same but their
shapes are changed somewhat by mixing.
- In the early part of the second period diatomics (B2, C2, N2), the MO of
sg orbitals formed from 2pz orbitals is higher in energy than the pu
orbitals formed from the 2px and 2py orbitals.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/125p
 Orbital Mixing
MO of O2 Molecule

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/125p
Diatomic Molecules of the 1st & 2nd Periods
Paramagnetic: Attracted by magnetic field, unpaired electrons
Diamagnetic: Repelled by magnetic field, paired electrons
- The energy of all the orbitals decreases
as the increased nuclear charge attracts
the electrons more strongly.
- H2 (bond order: 1)
- He2 (bond order: 0)
- Li2 (bond order: 1)
- Be2 (bond order: 0)
- B2 (bond order: 1, paramagnetic)
- C2 (bond order: 2, diamagnetic)
- N2 (bond order: 3, diamagnetic)
- O2 (bond order: 2, paramagnetic)
- F2 (bond order: 1)
Copyright© 2000 by Houghton 12
Mifflin Company. All rights reserved.
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/126p
Diatomic Molecules of the 1st & 2nd Periods
- Beginning at the left, as the number of electrons increases, the number in
bonding orbitals also increases, the bond strength becomes greater, and
the bond length becomes shorter. From N2, the trend reverses.
- r(N)>r(O)>r(F), d(N-N)<d(O-O)<d(F-F). The bond order is important.

Gary L. Miessler, Paul J. Fischer, Donald A.

Tarr./Inorganic chemistry: INTERNATIONAL
EDITION /PESRSON/FIFTH
EDITION/2013/128~130p
Copyright© 2000 by Houghton 13
Diatomic Molecules of the 1st & 2nd Periods
- The bond order determines the bond length and the bond strength.

Gary L. Miessler, Paul J. Fischer, Donald A.

Tarr./Inorganic chemistry: INTERNATIONAL EDITION
/PESRSON/FIFTH EDITION/2013/131p
 Photoelectron Spectroscopy
- The energies of electrons in orbitals can be determined from photoelectron
spectroscopy.

- The lower energy peaks are for the

higher energy orbitals.
- The observed energies can be directly
correlated with the molecular orbital
energies.
- The spectrum shows the interaction
of the electronic energy with the
vibrational energy.
- Orbitals that are strongly involved in
bonding have vibrational fine structure.
- Orbitals less involved in bonding have
Copyright© 2000 by Houghton 15
only a few individual peaks atCompany.
Mifflin each level.
All rights reserved.
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/132p
Heteronuclear Diatomic Molecules
- Noncrossing rule: Orbitals of the same symmetry interact so that their
energies never cross.
- A greater nuclear charge on one of the atoms lowers its atomic energy
levels and shifts the resulting molecular orbital levels.
- The potential energy steadily
becomes more negative from left
to right within a period, as the
increasing nuclear charge attracts
more strongly.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/133,134p
 Carbon Monoxide
- For heteronuclear molecules, a given MO receives unequal contributions
from the AOs. Gary L. Miessler, Paul J. Fischer, Donald A.
Tarr./Inorganic chemistry: INTERNATIONAL
EDITION /PESRSON/FIFTH EDITION/2013/135p

- The AO closer in energy to an MO

contributes more to the MO and its
coefficient is larger in the wave
functions
Carbon monoxide
: The more electronegative element
has AOs at lower potential energies
than the less electronegative element.
- Like N2, the pu(2p) orbitals are lower
in energy than the sg(2p).
- The bonding orbital 2s has more
contribution from the lower energy
Copyright© 2000 by Houghton 17
oxygen 2s AO. Mifflin Company. All rights reserved.
 Frontier Orbitals
- Frontier orbitals:
The highest occupied molecular orbital (HOMO)
The lowest unoccupied molecular orbital (LUMO)

- The HOMO of CO is 3s with a higher electron density and a larger

lobe on the carbon. The lone pair in this orbital forms a bond with a
vacant orbital on metal. M-C-O.
- Bonding MOs have a greater contribution from the lower energy AO,
and their electron density is concentrated on the atom with the lower
energy level or higher electronegativity.
- The higher energy carbon pz orbital has significant contribution to 3s
MO.
- The LUMOs of CO are the 1p* orbitals and are concentrated on carbon.
- The frontier orbitals can contribute electrons or accept electrons in
reactions.
Ionic Compounds & Molecular Orbitals
- Ionic compound can be considered the limiting form of polarity in
heteronuclear diatomic molecules.
- At limit, the electron is transferred completely to the more electronegative
atom to form a negative ion, leaving a positive ion with a high energy vacant
orbital.
- In LiF, the electron from the Li 2s orbital is transferred to the bonding orbital
formed from interaction between the Li 2s orbital and the F 2pz orbital.

negative

Lattice
Copyright© 2000enthalpy
by Houghtonis large
enough to overcome19 all
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/138,139p the endothermic processes and the negative DS.
Mifflin Company. All rights reserved.
Molecular Orbitals for Larger Molecules
Group orbital: collections of matching orbitals on outer atoms
- These group orbitals should be viewed as collections of orbitals
that potentially could interact with central atom orbital.

The potential energy of the H

1s orbital is a much better
match for the F 2pz orbitals
than their 2s orbitals.
The interaction with the 2pz
is much stronger than that
with the 2s.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/140,141p
Molecular Orbitals for Larger Molecules
Two electrons occupy a low-
energy orbital formed by the
interaction of all three atoms
(a 3-center, 2-electron bond).

In general, bonding orbitals

derived from three or more
atoms usually have lower
energies than those that include
orbitals from only two atoms,
but the total energy of a a
molecule is the sum of the
energies of all of the electrons in
all the orbitals.
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:
INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/142p
Molecular Orbitals for Larger Molecules
CO2; SALC: symmetry-adapted linear combinations of the orbitals

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/143p
Molecular Orbitals for Larger Molecules
CO2; SALC: symmetry-adapted linear combinations of the orbitals
The process used in creating MOs is to match the symmetries of the group
orbitals, using their irreducible representations with the symmetries of the
central atom orbitals. If the symmetries match and the energies are similar,
there is an interaction.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/144p
Molecular Orbitals for Larger Molecules

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/144,145p

The character table of this group

shows the symmetry of these orbitals.
Molecular Orbitals for Larger Molecules

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/145, 146p

The 2s and 2pz orbitals of carbon have two possible sets of group .
Molecular Orbitals for Larger Molecules
- The energy match between group
orbital 3 and C 2s orbital is much
better than that between group
orbital 1 and C 2s orbital.
- The C 2py orbital can interact
with group orbital 5. The C 2px
orbital interacts with group
orbital 7.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/146,147p
Molecular Orbitals for Larger Molecules

- The 16 valence electrons

occupy from bottom, two
nonbonding s orbitals, two
bonding s orbitals, two
bonding p orbitals, two
nonbonding p orbitals.
- There are four bonds in the
CO2 molecule.
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/147,148p
 Hybrid Orbitals
- The AOs that combine to form MO as hybrid orbital.
- Hybrid orbitals are localized in space and are directional, pointing in a
specific direction. These hybrid orbitals point from a central atom
toward surrounding atoms or lone pairs.
- Methane, CH4: G = A1 + T2 (s + 3p = sp3 hybrid)

- NH3 and H2O molecules have sp3 hybrid with

small bond angle due to the repulsion by lone
pair.
- CO2 uses sp hybrids and SO3 uses sp2 hybrids for
s bonds.
- p orbitals not used in hybrids are available for p
Gary L. Miessler, Paul J. Fischer, Donald A.
Tarr./Inorganic chemistry: INTERNATIONAL EDITION
/PESRSON/FIFTH EDITION/2013/162p
interactions.
Hybrid Orbitals
- Hybridization uses vectors
pointing toward the outlying
atoms and usually deals only
with s bonding. Once the s
hybrids are known, p bonding is
added, using orbitals that do not
participate in the hybridization.

- Hybridization may be quicker

than the MO approach, because
the MO approach uses all the
AOs of the atoms and includes
both s and p bonding directly.

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry:

INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/163p
 Hybrid Orbitals

Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/163,164p