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Intensity‐carrying modes important for vibrational polarizabilities and hyperpolarizabilities of molecules: Derivation from the algebraic properties of formulas and applications
Author(s) -
Torii Hajime
Publication year - 2002
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10097
Subject(s) - polyene , hyperpolarizability , polarizability , chemistry , dipole , computational chemistry , molecule , electronegativity , intermolecular force , polarization (electrochemistry) , basis (linear algebra) , algebraic number , molecular physics , valence (chemistry) , chemical physics , mathematics , organic chemistry , mathematical analysis , geometry
The intensity‐carrying mode (ICM) theory is developed for analyzing the vibrational motions that mainly contribute to vibrational polarizabilities and hyperpolarizabilities, which are important for describing intermolecular electrostatic interactions and nonlinear optical properties of molecules. The ICMs are derived from dipole derivatives, polarizability derivatives, and first hyperpolarizability derivatives by using algebraic properties of intensity formulas. The way to obtain explicit forms of ICMs, including the optimization method of the basis of the ICM vector space, is discussed in detail. One‐ and two‐dimensional models are constructed on the basis of the ICMs. The theory is applied to three molecules (a push–pull type polyene, a streptocyanine dye cation, and a symmetric neutral polyene) taken as typical examples. It is shown that the ICM theory provides a reasonable picture on the vibrational polarization properties of these molecules. On the basis of this result, the validity of the valence‐bond charge transfer (VB‐CT) model, which is a one‐dimensional model and is widely used to describe the electronic and vibrational properties of dye molecules, is also discussed. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 997–1006, 2002