Mixed Quantum-Classical Molecular Dynamics Study of the Hydroxyl Stretch in Methanol/Carbon-Tetrachloride Mixtures II: Excited State Hydrogen Bonding Structure and Dynamics, Infrared Emission Spectrum
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- 作者：Kijeong Kwac ; Eitan Geva
- 刊名：The Journal of Physical Chemistry B
- 出版年：2012
- 出版时间：March 8, 2012
- 年：2012
- 卷：116
- 期：9
- 页码：2856-2866
- 全文大小：509K
- 年卷期：v.116,no.9(March 8, 2012)
- ISSN：1520-5207
文摘
We present a mixed quantum-classical molecular dynamics study of the hydrogen-bonding structure and dynamics of a vibrationally excited hydroxyl stretch in methanol/carbon-tetrachloride mixtures. The adiabatic Hamiltonian of the quantum-mechanical hydroxyl is diagonalized on-the-fly to obtain the ground and first-excited adiabatic energy levels and wave functions which depend parametrically on the instantaneous configuration of the classical degrees of freedom. The dynamics of the classical degrees of freedom are determined by Hellmann鈥揊eynman forces obtained by taking the expectation value of the force with respect to the ground or excited vibrational wave functions. Polarizable force fields are used which were previously shown to reproduce the experimental infrared absorption spectrum rather well, for different isotopomers and over a wide composition range [Kwac, K.; Geva, E. J. Phys. Chem. B2011, 115, 9184]. We show that the agreement of the absorption spectra with experiment can be further improved by accounting for the dependence of the dipole moment derivatives on the configuration of the classical degrees of freedom. We find that the propensity of a methanol molecule to form hydrogen bonds increases upon photoexcitation of its hydroxyl stretch, thereby leading to a sizable red-shift of the corresponding emission spectrum relative to the absorption spectrum. Treating the relaxation from the first excited to the ground state as a nonadiabatic process, and calculating its rate within the framework of Fermi鈥檚 golden rule and the harmonic-Schofield quantum correction factor, we were able to predict a lifetime which is of the same order of magnitude as the experimental value. The experimental dependence of the lifetime on the transition frequency is also reproduced. Nonlinear mapping relations between the hydroxyl transition frequency and bond length in the excited state and the electric field along the hydroxyl bond axis are established. These mapping relations make it possible to reduce the computational cost of the mixed quantum-classical treatment to that of a fully classical treatment.