Theoretical study of hydrogen and deuterium bond in glutaric acid crystal dimer

Abstract

AbstractIn the spirit of the work of Blaise et al. [J Chem Phys, 2005, 122, 64306], we have extended their quantum theoretical approach by accounting for the intrinsic anharmonicity of the slow frequency mode, which is described by a Morse potential to reproduce the polarized infrared line shapes of glutaric acid dimer and its deuterium derivative at different temperatures. In this approach, the adiabatic approximation is performed for each separate H‐bond bridge of the dimer, and a strong nonadiabatic correction is introduced into the model via the resonant exchange between the fast mode excited states of the two moieties. Working within the strong anharmonic coupling theory, according to which the high‐frequency mode is anharmonically coupled to the H‐bond bridge, this approach incorporated the Davydov coupling between the excited states of the two moieties, the quantum direct and indirect dampings and the intrinsic anharmonicity of the H‐bond bridge. The spectral density was obtained within the linear response theory by Fourier transform of the damped autocorrelation functions. The numerical results show that the theoretical line shapes of the glutaric acid dimer are in fairly good agreement with the experimental ones. Using a minimum number of independent parameters, this theoretical approach fits correctly the experimental line shapes of the glutaric acid dimer. The effects of deuteration and temperature have been successfully reproduced by our calculations. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012