Infrared spectra of 1.3-dithiole-2-thione and its selenium analogues ând frequency assignment and molecular force constants

Infrared spectra of 1,3-dithiole-2-thione (DTT) and its four selenium analogues have been studied in the region 4000 to 20 cm�1. Assignment of all the fundamental frequencies was made by noting the band shifts on progressive selenation. Normal coordinate analysis procedures have been applied for both in-plane and out-of-plane vibrations to help the assignments. The Urey�Bradley force function supplemented with valence force constants for the out-of-plane vibrations was employed for coordinate calculations. A correlation of the infrared assignments of DTT with its different selenium analogues is accomplished. Further, the infrared assignments are compared with those of trithiocarbonate ion and its selenium analogues and other structurally related heterocyclic molecules.

Force constants and thermodynamic functions of iodine heptafluoride

Normal coordinate analysis of a molecule of the type XY7 (point group D5h) has been carried out using Wilson's FG, matrix method and the results have been utilized to calculate the force constants of IF7 from the available Raman and infrared data. Some of the assignments made previously by Lord and others have been revised and with the revised assignments the thermodynamic quantities of IF7 have been computed from 300°K to 1000°K under rigid rotator and harmonic oscillator approximation.

Use of L matrix to obtain reliable ab initio force constants of polyatomic molecules: ethylene as a test system

Direct use of experimental eigenvalues of the vibrational secular equation on to the ab initio predicted eigenvector space is suggested as a means of obtaining a reliable set of intramolecular force constants. This method which we have termed RECOVES (recovery in the eigenvector space) is computationally simple and free from arbitrariness. The RECOVES force constants, by definition, reproduce the experimental vibrational frequencies of the parent molecule exactly. The ab initio calculations were carried out for ethylene as a test molecule and the force constants obtained by the present procedure also correctly predict the vibrational frequencies of the deuterated species. The RECOVES force constants for ethylene are compared with those obtained by using the SQM procedure.

SCF and electron correlation studies on structure, force constants and vibrational spectra of borane monoammoniate complex

Effects of basis set and electron correlation on the equilibrium geometry, force constants and vibrational spectra of BH3NH3 have been studied. A series of basis sets ranging from double zeta to triple zeta including polarization and diffuse functions have been utilized. All the SCF based calculations overestimate the dative B-N bond distance and considerable improvement occurs when the treatment for electron correlation is introduced. Detailed vibrational analysis for BH3NH3 has been carried out. The mean absolute percentage deviation of the ab initio predicted vibration frequencies of (BH3NH3)-B-11 from the experiment is about 10% for the SCF based calculations and the MP2 method shows better agreement, the overall deviation being 5-6%. The ground state effective force constants of BH3NH3 were obtained using RECOVES procedure. The RECOVES sets of force constants are found to be highly satisfactory for the prediction of the vibrational frequencies of different isotopomers of BH3NH3. The mean absolute percentage deviation of the calculated frequencies of different isotopomers from the experiment is much less than 1%. The RECOVES-MP2/augDZP set of force constants was found to be the best set among the different sets for this molecule. Theoretical infrared intensities are in fair agreement with the observed spectral features.

Vibrational force constant and electron relaxation in H2 and Li2

The force constants of H2 and Li2 are evaluated employing their extended Hartree-Fock wavefunctions by a polynomial fit of their force curves. It is suggested that, based on incomplete multiconfiguration Hartree-Fock wavefunctions, force constants calculated from the energy derivatives are numerically more accurate than those obtained from the derivatives of the Hellmann-Feynman forces. It is observed that electrons relax during the nuclear vibrations in such a fashion as to facilitate the nuclear motions.

Assignment of fundamental vibrations of. ,N'-dimethylthiourea,

The infrared spectra of symmetric N,N′-dimethylthiourea (s-DMTU) and its N-deuterated (s-DMTU-d2) species have been measured. The fundamental frequencies have been assigned by comparison with the assignments in structurally related molecules and the infrared band shifts on N-deuteration, S-methylation, available Raman data and with the aid of theoretical band assignments from normal coordinate treatments for s-DMTU-d0 and -d2. A force field is derived for s-DMTU by transferring the force constants chiefly from N-methylthiourea and the subsequent refinement of the force constants by a least squares procedure.

Conformational Characterization of S-Methyl Dithiocarbazate by Infrared Spectra and Vibrational Assignments

Infrared spectra are recorded for S-methyl dithiocarbazate and its N-deuterated compound in two molecular conformations in the solid state and in solution between 4000 and 30 cm−1. The assignments have been supported from a complete normal coordinate analysis; the conformation sensitive bands of the –CSNHNH2 grouping are discussed. The assignments are compared with those of related molecules to check the internal consistency and to obtain the pattern of the characteristic bands of thiocarbazoyl (–CSNHNH2) group. The magnitudes of the C–N and S–CH3 torsional barriers are estimated from the force constants.

Vibrational spectra of imidazoline-2-thione and imidazoline-2-one

Raman and infrared spectra of imidazoline-2-thione (IMZT) and imidazoline-2-one (IMZO) have been recorded. Normal coordinate analyses have been performed for all the fundamental vibrations of IMZT, IMZT-d2 and IMZO employing a Urey—Bradley potential function supplemented with valence type force constants for the out of plane modes. The results of the vibrational analyses are discussed in relation to the assignments in related molecules. The vibrational assignments for IMZT and IMZO have been compared with those in structurally similar molecules and the need to obtain more reliable band assignments for some of the molecules considered is emphasised.

Electronic Structure of some Substituted azolidines.CNDO/2, NMR and vibratational spectoroscopic studies

The 1H and 13C chemical shifts, characteristic vibrational frequencies and force constants for some substituted azolidines are correlated with the results of the CNDO/2 calculations. The influence of the exo and endo heteroatoms on the electronic structure of the heterocyclic ring are discussed.

Molecular vibrations and conformation of primary dithiocarbamate ester. Infrared and NMR studies on S-methyl dithiocarbamate

The i.r. spectra of a primary dithiocarbamate ester namely, S-methyl dithiocarbamate (SMDTC) and its N-dideuterated compound have been measured between 4000 and 30 cm−1. Spectra in solution and at liquid nitrogen temperature have also been obtained. Assignment of all the fundamentals has been proposed and supported from a full normal coordinate analysis. The band assignments for SMDTC have been compared with those of related molecules and the characteristic bands of primary thioamides are derived. Conformational flexibility of SMDTC has been examined by i.r. and proton NMR spectroscopy. The hindered rotation around the C---N bond has been studied by a complete line shape analysis. The magnitude of ---NH2 and ---CH3 torsional barriers is also estimated from vibrational frequencies and force constants.

A Reinvestigation of the Normal Vibrations of Thioacetamide

The normal coordinate treatments of thioacetamide and its seven isotopic molecules have been carried out using Urey-Bradley force constants refined by a least-squares procedure. The laser Raman spectrum of thioacetamide has also been recorded.

Lattice dynamics of hexagonal ice

The lattice dynamics of hexagonal ice is worked out with the force constants deduced from the experimental elastic constants.

Urey-Bradley potential function for the in-plane vibrations of boric acid

The Urey-Bradley force constants for the in-plane vibrations of the boric acid molecule are calculated using the Wilson's F-G matrix method. They are as follows: KO-H=5·23, KB-O=4·94, HBOH=0·36, {Mathematical expression}, F00=0·68 and FBH=0·98 in units of 105 dynes/cm. Using the force constants, the frequencies are recalculated and the calculated values agree with the observed values satisfactorily. The in-plane vibrational frequencies of deuterated boric acid are also calculated and again satisfactory agreement with the observed values is found.