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A new way of analyzing vibrational spectra. III. Characterization of normal vibrational modes in terms of internal vibrational modes
Author(s) -
Konkoli Zoran,
Cremer Dieter
Publication year - 1998
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1998)67:1<29::aid-qua3>3.0.co;2-0
Subject(s) - normal mode , hot band , molecular vibration , vibrational spectrum , characterization (materials science) , chemistry , spectral line , vibrational partition function , molecular physics , computational chemistry , materials science , physics , vibration , molecule , nanotechnology , quantum mechanics , organic chemistry
The concept of characterizing normal vibrational modes l μ in terms of internal vibrational modes v n typical of molecular fragments or structural subunits is developed. Essential for this concept is the amplitude n μ that provides the basis for a quantitative comparison of modes l μ and v n and, by this, facilitates the extraction of chemical information out of vibrational spectra. Twelve possibilities of defining amplitude are tested with regard to (a) the physical basis of the definition of , (b) the dependence of on the set of internal parameters chosen to describe the molecule, and (c) the amount of chemical information transferred by . The two most promising candidates for a generally applicable amplitude are based on adiabatic internal modes and a comparison of l μ and v n with the help of mass or force constant matrix. For the practical testing of amplitude , three different criteria are developed. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67 : 29–40, 1998