Dynamic treatment of vibrational energy relaxation in a heterogeneous and fluctuating environment

Physics – Chemical Physics

Scientific paper

Rate now

  [ 0.00 ] – not rated yet Voters 0   Comments 0

Details

24 pages, 7 figures, submitted to J. Chem. Phys

Scientific paper

10.1063/1.2985606

A computational approach to describe the energy relaxation of a high-frequency vibrational mode in a fluctuating heterogeneous environment is outlined. Extending previous work [H. Fujisaki, Y. Zhang, and J.E. Straub, J. Chem. Phys. {\bf 124}, 144910 (2006)], second-order time-dependent perturbation theory is employed which includes the fluctuations of the parameters in the Hamiltonian within the vibrational adiabatic approximation. This means that the time-dependent vibrational frequencies along an MD trajectory are obtained via a partial geometry optimization of the solute with fixed solvent and a subsequent normal mode calculation. Adopting the amide I mode of N-methylacetamide in heavy water as a test problem, it is shown that the inclusion of dynamic fluctuations may significantly change the vibrational energy relaxation. In particular, it is found that relaxation occurs in two phases, because for short times ($\lesssim$ 200 fs) the spectral density appears continuous due to the frequency-time uncertainty relation, while at longer times the discrete nature of the bath becomes apparent. Considering the excellent agreement between theory and experiment, it is speculated if this behavior can explain the experimentally obtained biphasic relaxation the amide I mode of N-methylacetamide.

No associations

LandOfFree

Say what you really think

Search LandOfFree.com for scientists and scientific papers. Rate them and share your experience with other people.

Rating

Dynamic treatment of vibrational energy relaxation in a heterogeneous and fluctuating environment does not yet have a rating. At this time, there are no reviews or comments for this scientific paper.

If you have personal experience with Dynamic treatment of vibrational energy relaxation in a heterogeneous and fluctuating environment, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Dynamic treatment of vibrational energy relaxation in a heterogeneous and fluctuating environment will most certainly appreciate the feedback.

Rate now

     

Profile ID: LFWR-SCP-O-687369

  Search
All data on this website is collected from public sources. Our data reflects the most accurate information available at the time of publication.