Collective solvent coordinates for the infrared spectrum of HOD in D2O based on an ab initio electrostatic map

T Hayashi, TL Jansen, W Zhuang, S Mukamel*

*Bijbehorende auteur voor dit werk

OnderzoeksoutputAcademicpeer review

144 Citaten (Scopus)


An ab initio MP2 vibrational Hamiltonian of HOD in an external electrostatic potential parametrized by the electric field and its gradient-tensor is constructed. By combining it with the fluctuating electric field induced by the D2O solvent obtained from molecular dynamics simulations, we calculate the infrared absorption of the O-H stretch. The resulting solvent shift and infrared line shape for three force fields (TIP4P, SPC/E, and SW) are in good agreement with the experiment. A collective coordinate response for the solvent effect is constructed by identifying the main electrostatic field and gradient components contributing to the line shape. This allows a realistic stochastic Liouville equation simulation of the line shapes which is not restricted to Gaussian frequency fluctuations.

Originele taal-2English
Pagina's (van-tot)64-82
Aantal pagina's19
TijdschriftThe Journal of Physical Chemistry A
Nummer van het tijdschrift1
StatusPublished - 13-jan-2005

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