Premium
Influence of self‐association and inter‐molecular hydrogen bonding on the ν(C N) stretching mode of CH 3 C N and C 2 H 5 C N in binary mixtures with CH 3 OHA comparative study via concentration‐dependent polarized Raman study and ab initio calculation
Author(s) -
Srivastava Sunil K.,
Ojha Animesh K.,
Raghuvansh P.,
Kiefer W.,
Asthana B. P.
Publication year - 2006
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1550
Subject(s) - raman spectroscopy , chemistry , wavenumber , hydrogen bond , dephasing , molecule , ab initio quantum chemistry methods , analytical chemistry (journal) , binary number , ab initio , crystallography , chromatography , organic chemistry , physics , optics , arithmetic , mathematics , quantum mechanics
A Raman study of neat CH 3 C N and C 2 H 5 C N and their binary mixtures (CH 3 C N + CH 3 OH) and (C 2 H 5 C N + CH 3 OH) has been made using a scanning multichannel detection technique, which is also more precise, especially when the observed Raman line profile has multiple components. The spectra in the ν(C N) stretching region (2220–2280 cm −1 ) for both the reference systems were recorded with varying mole fractions of the reference molecule, CH 3 C N/C 2 H 5 C N, from 0.9 to 0.1. Ab initio calculations on the optimized structure and wavenumber position of the ν(C N) stretching mode of neat CH 3 C N and C 2 H 5 C N and their self‐associated and hydrogen‐bonded complex reveal that the wavenumber position of the ν(C N) stretching mode is shifted towards higher Raman wavenumbers because of both self‐association and the hydrogen‐bonded complex. This shift has been explained in terms of the repulsive interaction between the solute and solvent molecules. The dephasing of ν(C N) stretching mode with concentration shows that the viscosity dependent contribution is much more prominent than that due to concentration fluctuation. Copyright © 2006 John Wiley & Sons, Ltd.