Abstract
The problem of a comparison of quantum chemical calculation results with the experimental characteristics of molecules is discussed, and it is noted that the accuracy of quantum computations can be most fully evaluated by a comparison of the theoretical results with the experimental spectra. By means of calculations, the contribution of anharmonism to the theoretical values of absorption band intensities in the IR spectra of 15 fluoro and 36 chloro derivatives of hydrocarbons is estimated. The first and second derivatives of the molecular dipole moment are obtained by ab initio quantum chemical calculations with the use of the 6–31G(1d) basis set and allowance for electron correlations by the second order Möller-Plesset method. The performed calculation well reproduces the positions of maxima and the intensity ratio of fundamental, overtone, and complex absorption bands.
Similar content being viewed by others
References
G. M. Zhislin, Tr. Mosk. Matem. Obshch., 9, 82–120 (1960).
G. M. Zhislin, Teor. Matem. Fiz., 7, No. 3, 332–341 (1971).
M. A. Antonets, G. M. Zhislin, and P. A. Shereshevskii, Teor. Matem. Fiz., 16, No. 2, 235–246 (1973).
S. A. Vugal’ter and G. M. Zhislin, Teor. Matem. Fiz., 55, No. 1, 66–77 (1983).
L. A. Gribov, V. I. Baranov, and M. I. El’yashberg, Reference-Free Molecular Spectral Analysis [in Russian], URSS, Moscow (2002).
L. A. Gribov and V. I. Baranov, Theory and Methods for the Calculation of Molecular Processes: Spectra, Chemical Transformations and Molecular Logic [in Russian], KomKniga/URSS, Moscow (2006).
G. Herzberg, Vibrational and Rotational Spectra of Polyatomic Molecules, Van Nostrand, New York (1945).
S. Califano, Vibrational State, Willay and Sons, London (1976).
P. R. Bunker, Molecular Symmetry and Spectroscopy, Academic Press, New York (1979).
L. A. Gribov and W. J. Orville-Thomas, Theory and Methods of Calculation of Molecular Spectra, John Willey and Sons, Chichester, New York (1988).
L. A. Gribov, V. I. Baranov, and A. I. Pavlyuchko, Variation Methods to Solve Anharmonic Problems in the Theory of Molecular Vibrational Spectra [in Russian], Nauka, Moscow (1998).
L. A. Gribov and V. I. Baranov, Vibrations of Molecules [in Russian], URSS, Moscow (2008).
A. I. Pavlyuchko and L. A. Gribov, J. Struct. Chem., 51, No. 3, 444–452 (2010).
L. A. Gribov, A. I. Pavlyuchko, and E. V. Vasil’ev, Zh. Analit. Khim., 65, No. 11, 1135–1138 (2010).
M. W. Schmidt, K. K. Baldridge, J. A. Boatz et al., J. Comput. Chem., 14, 1347–1363 (1993).
Site of the US National Institute of Standards, http://webbook.nist.gov/chemistry/
L. A. Gribov, I. A. Novakov, A. I. Pavlyuchko, and O. Yu. Shumovskii, J. Struct. Chem., 48, No. 3, 400–406 (2007).
L. A. Gribov, I. A. Novakov, A. I. Pavlyuchko, and E. V. Vasiliev, J. Struct. Chem., 47, No. 4, 635–641 (2006).
L. A. Gribov, I. A. Novakov, A. I. Pavlyuchko, and E. V. Vasiliev, J. Struct. Chem., 48, No. 4, 600–606 (2007).
B. V. Ioffe, R. R. Kostikov, and V. V. Razin, Physical Methods to Determine the Structure of Organic Compounds [in Russian], Vysshaya Shkola, Moscow (1984).
Author information
Authors and Affiliations
Corresponding author
Additional information
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 51, No. 6, pp. 1084–1090, November–December, 2010.
Original Russian Text Copyright © 2010 by A. I. Pavlyuchko, E. V. Vasiliev, and L. A. Gribov
Rights and permissions
About this article
Cite this article
Pavlyuchko, A.I., Vasiliev, E.V. & Gribov, L.A. Quantum chemical estimation of the overtone contribution to the IR spectra of hydrocarbon halogen derivatives. J Struct Chem 51, 1045–1051 (2010). https://doi.org/10.1007/s10947-010-0161-5
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10947-010-0161-5