Estimation of bond-bending force constants in tetrahedral semiconductors and their variation with pressure obtained from spectroscopic data

1974 ◽  
Vol 10 (10) ◽  
pp. 4222-4227 ◽  
Author(s):  
J. A. Van Vechten
1966 ◽  
Vol 21 (9) ◽  
pp. 1377-1384
Author(s):  
A. V. Willi

Kinetic carbon-13 and deuterium isotope effects are calculated for the SN2 reaction of CH3I with CN-. The normal vibrational frequencies of CH3I, the transition state I · · · CH3 · · · CN, and the corresponding isotope substituted reactants and transition states are evaluated from the force constants by solving the secular equation on an IBM 7094 computer.Values for 7 force constants of the planar CH3 moiety in the transition state (with an sp2 C atom) are obtained by comparison with suitable stable molecules. The stretching force constants related to the bonds being broken or newly formed (fCC, fCC and the interaction between these two stretches, /12) are chosen in such a way that either a zero or imaginary value for νʟ≠ will result. Agreement between calculated and experimental methyl-C13 isotope effects (k12/ k13) can be obtained only in sample calculations with sufficiently large values of f12 which lead to imaginary νʟ≠ values. Furthermore, the difference between fCI and fCC must be small (in the order of 1 mdyn/Å). The bending force constants, fHCI and fHCC, exert relatively little influence on k12/k13. They are important for the D isotope effect, however. As soon as experimental data on kH/kD are available it will be possible to derive a value for fHCC in the transition state if fHCI is kept constant at 0.205 mdynA, and if fCI, fCC and f12 are held in a reasonable order of magnitude. There is no agreement between experimental and calculated cyanide-C13 isotope effects. Possible explanations are discussed. — Since fCI and fCC cannot differ much it must be concluded that the transition state is relatively “symmetric”, with approximately equal amounts of bond making and bond breaking.


2004 ◽  
Vol 82 (6) ◽  
pp. 998-1005
Author(s):  
Rafael Escribano ◽  
Ismael K Ortega ◽  
Rafael G Mosteo ◽  
Pedro C Gómez

A number of bromine oxides and mixed chlorine–bromine oxides for which spectroscopic information is available have been chosen to investigate the nature and characteristics of the Br—O bond. The study consists of the empirical determination of stretching force constants for these bonds from observed vibrational spectroscopic data and the analysis of the topological characteristics of the bonds via ab initio calculations. The latter have been performed at the MP2 level with a 6-311+G(2df) basis set, to provide a uniform and systematic framework for comparing these species. Three types of Br—O bonds have been found, with different characteristics of strength and electron density. The results are compared with those recently found for the Cl—O bond in chlorine oxides.Key words: bromine oxides, bond electronic structure.


1983 ◽  
Vol 61 (2) ◽  
pp. 263-266 ◽  
Author(s):  
A. Annamalai ◽  
Surjit Singh

The redundancy-free internal valence force field of monomeric acetic acid is evaluated using CNDO/force calculations and least-squares refinement. The initial force field is set up by taking the interaction and bending force constants from CNDO force field and transferring the stretching force constants from the force fields of chemically related molecules. Vibrational frequencies of monomeric CH3COOH, CH3COOD, CD3COOH, and CD3COOD are used to refine the force constants. The experimental force field thus obtained is found to be reasonable when compared to the force fields of related molecules as well as on the basis of the frequency fits and potential energy distributions.


1980 ◽  
Vol 58 (3) ◽  
pp. 351-358 ◽  
Author(s):  
M. S. Kushwaha ◽  
S. S. Kushwaha

An eight-parameter bond-bending force model (BBFM), recently developed by us for zinc-blende (ZB) structure, has been used to study the lattice dynamics of other compounds of the II–VI and III–V groups. The model parameters were calculated using six critical point phonon frequencies, two elastic constants, and the lattice equilibrium condition. Phonon dispersion curves, phonon density of states, and Debye-characteristic temperatures have been calculated. The comparison of theoretical and the available experimental results reveals a fairly good agreement. The merits and demerits of the present model have been discussed in full.


1970 ◽  
Vol 23 (5) ◽  
pp. 881 ◽  
Author(s):  
SN Rai ◽  
SN Thakur

The F-matrix elements for the two-dimensional symmetry species are dependent on one arbitrary parameter in addition to the vibrational frequencies. This parameter has been chosen as an angle � (0 ≤ � ≤ 2π) and the F-matrix elements for the A1- and the E-species of trihalides of phosphorus and arsenic have been studied as functions of �. It is found that the best values of the force constants obtained from Coriolis 1; constants can be correlated with those values of the angle ξ for which the bending force constant exhibits a minimum.


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