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A new way of analyzing vibrational spectra. IV. Application and testing of adiabatic modes within the concept of the characterization of normal modes
Author(s) -
Konkoli Zoran,
Larsson J. Andreas,
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<41::aid-qua4>3.0.co;2-z
Subject(s) - adiabatic process , molecular vibration , normal mode , amplitude , spectral line , chemistry , symmetry (geometry) , metric (unit) , coupling (piping) , molecule , molecular physics , computational chemistry , physics , vibration , quantum mechanics , mathematics , geometry , materials science , operations management , economics , metallurgy
The CNM (characterization of normal modes) method for extracting chemical information out of vibrational spectra is tested for vibrational spectra of molecules with relatively strong or relatively weak coupling between internal vibrational modes. Symmetry, parameter set stability, and frequency uncertainty tests are applied to check whether internal vibrational modes, internal mode frequencies, and amplitudes n μ comply with symmetry, are independent of the set of internal parameters ζ n used to describe molecular geometry or fulfill a Lorentzian correlation between amplitudes n μ and frequency differences Δω n μ =ω n −ω μ . In all cases considered, amplitudes n μ based on adiabatic internal modes and mass or force constant matrices as metric O are superior to any other definition of amplitude. They represent the basic elements of the new CNM method that leads to chemically reasonable results and presents a new way of extracting chemical information out of vibrational spectra. A number of deficiencies of the potential energy distribution (PED) analysis is discussed. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67 : 41–55, 1998