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In this paper, we present simulations of the decay of quantum coherence between vibrational states of I2 in its ground (X) electronic state embedded in a cryogenic Kr matrix. We employ a numerical method based on the semiclassical limit of the quantum Liouville equation, which allows the simulation of the evolution and decay of quantum vibrational coherence using classical trajectories and ensemble averaging. The vibrational level-dependent interaction of the I2(X) oscillator with the rare-gas environment is modeled using a recently developed method for constructing state-dependent many-body potentials for quantum vibrations in a many-body classical environment [J. M. Riga, E. Fredj, and C. C. Martens, J. Chem. Phys. 122, 174107 (2005)]. The vibrational dephasing rates γ0n for coherences prepared between the ground vibrational state |0> and excited vibrational state |n> are calculated as a function of n and lattice temperature T. Excellent agreement with recent experiments performed by Karavitis et al. [Phys. Chem. Chem. Phys. 7, 791 (2005)] is obtained. [ABSTRACT FROM AUTHOR]

In this paper, we present a method for constructing simple state-dependent many-body potentials for quantum vibrations in a classical bath. The approach is based on an adiabatic separation between high-frequency quantum vibrational modes of the solute and the lower frequency classical motion of the solvent, and on a first-order perturbation theory description of the dependence of the quantum energies on bath configuration. In the simplest realization of the method, the delocalized quantum probability density of the vibrational mode is approximated by a sum of two δ functions, with positions and weights chosen to represent the lowest three moments of the exact distribution. Thus, in the many-body description of the system, each atom describing the quantum vibration is represented by a pair of particles. These quantum particles are held in rigid relative position and interact with the bath via potentials the magnitudes of which are modified by the δ-function weights. The resulting approach allows the classical molecular dynamics of molecules in arbitrary quantum vibrational states to be simulated with a little more effort than a purely classical description. The applicability of the method is illustrated in many-body simulations of the dephasing of vibrational superposition states of I2 in a cryogenic krypton matrix, yielding results in good agreement with experiment. [ABSTRACT FROM AUTHOR]

In this paper we describe an application of the trajectory-based semiclassical Liouville method for modeling coherent molecular dynamics on multiple electronic surfaces to the treatment of the evolution and decay of quantum electronic coherence in many-body systems. We consider a model representing the coherent evolution of quantum wave packets on two excited electronic surfaces of a diatomic molecule in the gas phase and in rare gas solvent environments, ranging from small clusters to a cryogenic solid. For the gas phase system, the semiclassical trajectory method is shown to reproduce the evolution of the electronic–nuclear coherence nearly quantitatively. The dynamics of decoherence are then investigated for the solvated systems using the semiclassical approach. It is found that, although solvation in general leads to more rapid and extensive loss of quantum coherence, the details of the coupled system–bath dynamics are important, and in some cases the environment can preserve or even enhance quantum coherence beyond that seen in the isolated system. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]