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 MOHAMED IMRAN P K
 Lecturer (SG) in Chemistry

 Islamiah College, VANIYAMBADI

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 CONCEPTS
p
p
± NEWTONIAN
p
p
- QUANTUM
MECHANICS
 Only a Non-classical concept can allow
Carbon to form 5 bonds (Plasma
Chemistry ± Thermosphere)
 Heisenberg¶s Uncertainty Principle and
Einstein's Special Theory of Relativity are
the concepts in Non-classical Form
 Schrodinger¶s Wave Equation, of course
u times 3 is 3 times u
½

A times B is not B times A
of a 


This is one of the many things
that is addressed by

 

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 Orbitals of ³SYMMETRY´ are considered rather
than just Sigma or Pi Orbitals
 The wave functions for localised structure is
constructed based on assumptions and
approximations
 The MO¶s belonging to the same subgroup are
constrained to be mutually orthogonal while
those belonging to different subgroups are free
to overlap
The following approximations are considered

# CNDO
# CINDO
# MNDO
# MINDO
# LCAO
# Hartree-Fock SCF
# Moller-Plasset
The computer does the calculations
Here are some important properties

 Molecular orbital energies

 Total Electron and Nuclear Energies
 Heat of Formation
 Partial atomic charges (Mulliken Population analysis)
 Electrostatic Potentials
 Dipole moments
 Bond orders and valencies
 Vibrational Frequencies
 Atomic Electron Densities ± pi and sigma
 Exact stable geometry under a set of conditions
NEGATIVE HYPERCONJUGATION
 - The effect of donation of electron density from
filled ? or n?-orbitals to the symmetry adapted

*-orbital(s) of
-bond(s) of a molecular entity
resulting in building ?-character into bonds that
nominally possess only
-character. The
consequences of the effect are, for example, in
elongation of the C-F bond in the -fluoroethyl
anion and stabilization of the antiperiplanar
conformation of fluoromethylamine.
Pure Appl. Chem., Vol. 71, No. 10, pp. 1919-1981, 1999
 Hyperconjugation is ? 
or ?  pC
 Negative HC is ? or n? 
* (C---X)
Some of the important consequences of the negative hyperconjugation are

 The   of the AY bond in XnAY, where X is an

electronegative element, A is any hypervalent atom and
Y is any other atom or group attached to A
 The  
 in pi-orbital population of the X-atom and
hence an increase on charge of that atom
 m of the XAY angle e.g. 113 deg in place of 109
deg.
  of the AX bond
 And some changes in the geometrical properties
 The calculations for this system were done under the Cs symmetry
and the total charge on the Fluorine atoms are tabulated as below:
 ___________________________________________________
Total Charge Si-F bond length C-Si-F angle
 __________________________________________________
1. F -0.349 1.597 A 113.86 deg
 u. F -0.358 1.595 A 110.40 deg
 3. F -0.358 1.595 A 110.40 deg
 __________________________________________________
 Si-F bond length (theoretical) = 1.57 A
Our present picture of Physical reality,
particularly in relation to the nature of  ,
is due for a grand shake-up ± even
greater, perhaps, than that which has
already been provided by present-day
relativity and quantum mechanics.
Roger Penrose