Nonequilibrium molecular dynamics simulations of vibrational energy relaxation of HOD in D2O.

Understanding the Effects of Hydrogen Bonding at the Vapor-Water Interface: Vibrational Sum Frequency Spectroscopy of H2O/HOD/D2O Mixtures Studied Using Molecular Dynamics Simulations

Molecular structure and bonding interactions at the vapor-water interface of varying H2O/HOD/D2O composition has been calculated using molecular dynamics simulations. From these simulations a surface vibrational sum frequency (VSF) spectrum of the OH stretch region has been generated and compared with experimental VSF results of similar isotopic mixtures. The peak frequency of the uncoupled, so...

Molecular dynamics approach to vibrational energy relaxation: Quantum-classical versus purely classical nonequilibrium simulations

Energy relaxation versus spectral diffusion of the OH-stretching vibration of HOD in liquid-to-supercritical deuterated water.

The dynamics of vibrational energy relaxation (VER) of the OH-stretching vibration of HOD in liquid-to-supercritical heavy water is studied as a function of temperature and solvent density by femtosecond mid-infrared spectroscopy. Using the dielectric constant of the fluid both, the OH-stretching absorption frequency and the VER rate, can be correlated phenomenologically with the average hydrog...

Coherent Quantum Processes in Thermal and Nonequilibrium Environments

In this article, we describe recent work on investigating the role of the environment in influencing coherent quantum dynamics. We review numerical methodology based on a semiclassical limit of the quantum Liouville equation for simulating quantum coherent processes using classical-like molecular dynamics simulation and ensemble averaging and apply the approach to simulate vibrational dephasing...

Time-resolved infrared absorption studies of the solvent-dependent vibrational relaxation dynamics of chlorine dioxide.

We report a series of time-resolved infrared absorption studies on chlorine dioxide (OClO) dissolved in H2O, D2O, and acetonitrile. Following the photoexcitation at 401 nm, the evolution in optical density for frequencies corresponding to asymmetric stretch of OClO is measured with a time resolution of 120+/-50 fs. The experimentally determined optical-density evolution is compared with theoret...