Mixed quantum/classical approach, vibrational

A number of researchers [15, 38 40, 43, 113, 124 126, 128, 146] have used mixed quantum/classical models, mostly as described in Section III.A, to calculate vibrational line shapes for this system, and several are in fair agreement with experiment. Here we describe our latest work involving approaches discussed in Section III.C. Our theoretical line shapes are calculated as briefly described in previous sections and in published work [98]. From an MD simulation of SPC/E heavy water, we determine the electric field on each putative H atom. We then use electric field maps to determine the transition frequency and dipole derivative. The orientational contribution to mp(t) we... 

The mixed quantum classical description of EET can be achieved in using Eq. (49) together with the electronic ground-state classical path version of Eq. (50). As already indicated this approach is valid for any ratio between the excitonic coupling and the exciton vibrational interaction. If an ensemble average has been taken appropriately we may also expect the manifestation of electronic excitation energy dissipation and coherence decay, however, always in the limit of an infinite temperature approach. 

Linear and nonlinear infrared spectroscopy are powerful tools for probing the structure and vibrational dynamics of molecular systems." In order to take full advantage of them, however, accurate models and methods are required for simulating and interpreting spectra. A common approach for modeling spectra is based on computing optical response functions (ORFs)." Unfortunately, exact calculations of quantum-mechanical ORFs are not feasible for most systems of practical interest due to the large number of DOF. Instead, mixed quantum-classical methods ean provide suitable alternatives." " " ... 

We employ a classical description of the dynamical consequences of such a quantum object as the hydrogen bond. This concerns, for instance, the vibration of HB molecules. The price we pay for such an approach is that several fitted model parameters (e.g., force constants) are not related explicitly to the molecular structure of our object. Note that in the MD simulation method, based on application of various effective potentials, the classical theory is also often used [33-35]. Avery detailed analysis of the problems pertinent to the two-fractional (mixed) models of water is given in the latter work (review) with respect to various (mostly steady-state) properties of water. In the context of our work, the use of a classical mixed model is justified by a possibility of considering a simplified picture of two-state molecular motion allowing a relatively simple analytical calculation of the complex permittivity s(v) given in Section II. 

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