Infrared spectra of weak H-bonds: Fermi resonances and intrinsic anharmonicity of the H-bond bridge

被引：16

作者：

Belhayara, K ^{[1
]}

Chamma, D ^{[1
]}

Henri-Rousseau, O ^{[1
]}

机构：

[1] Univ Perpignan, Ctr Etude Fondamentales, F-66860 Perpignan, France

来源：

JOURNAL OF MOLECULAR STRUCTURE | 2003年 / 648卷 / 1-2期

关键词：

weak hydrogen bonds; Fermi resonances; Morse potential; non-adiabatic description; infrared spectral density; temperature and isotopic effects; direct relaxations; linear response theory; autocorrelation function;

D O I：

10.1016/S0022-2860(02)00618-X

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The present quantum theory is a new step in our attempt to obtain a flexible tool susceptible to be used by experimentalists working in the realm of the infrared spectra of the v(S)(X-(H) over right arrow ...Y) mode of weak strength hydrogen bonds. We take into account the intrinsic anharmonicity of the hydrogen bond stretching mode (X) over left arrow -H...(Y) over right arrow through a Morse potential by starting from a previous model [Chem. Phys. 248 (1999) 91] which described a weak hydrogen bond subject to a Fermi resonance and which included relaxation phenomena within a quantum treatment, but which considered this mode as an harmonic oscillator. The IR spectral density is studied within the linear response theory by Fourier transform of the autocorrelation function of the transition dipole moment operator of the X-H bond. The main feature brought by the anharmonicity of the H-bond bridge X-H...Y is the increase of the average frequency of the v(S)(X-(H) over right arrow ...Y) IR band upon a temperature rising. Then, this theory reproduces successfully the experimental behavior of both the first and second moments of this band which is observed when varying the temperature as well as upon isotopic substitution. (C) 2003 Elsevier Science B.V. All rights reserved.

引用

页码：93 / 106

页数：14

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