Viscosity dependence and solvent effects in the photoisomerization of cis-stilbene: Insight from a molecular dynamics study with an ab initio potential-energy functionThe photodissociation and photoisomerization of ICN in water is studied using molecular dynamics simulations. A water-ICN potential energy function that takes into account the different ground and excited state charges and their shift as a function of the reaction coordinate is developed. The calculations include nonadiabatic transitions between the different electronic states and allow for a complete description of the photodissociation leading to ground-state and excited-state iodine and to recombination producing ICN and INC. The calculated UV absorption spectrum, the cage escape probability, the quantum yield of ICN and INC, and the subsequent vibrational relaxation rate of ICN and INC are in reasonable agreement with recent experiments. The trajectories provide a detailed microscopic picture of the early events. For example, it is shown that most recombination events on the ground state involve nonadiabatic transitions before the molecule has a chance to completely dissociate on the excited state, and that the quantum yield for photoisomerization to form INC is statistically determined very early in the photodissociation process.

The photodissociation of ICN adsorbed at the liquid/vapor interface of water is studied using classical molecular dynamics with nonadiabatic surface hopping. The cage escape, geminate recombination to form ICN and INC and the subsequent vibrational relaxation of these two molecules (on their ground electronic states) is compared with the same process in bulk water and with previous photodissociation studies at liquid interfaces. We find that the reduced surface density and weaker solvent-solute interactions give rise to reduced rate of nonadiabatic transitions and that the probability for cage escape at the interface is significantly enhanced due to the possibility that one or both of the photodissociation fragments desorb into the gas phase. The overall desorption probability varies from 75% to 92% for ICN initially located just below the Gibbs surface (50% bulk density) to ICN located just above the Gibbs surface, respectively. The corresponding geminate recombination probabilities are 18% and 9%, respectively. The vibrational relaxation rate of the recombined ICN is slower than in the bulk by a factor of 2.3.

The thermodynamics and dynamics of a model S(N)1 reaction: t-BuCl --> t-Bu+ + Cl- is studied at the water liquid/vapor interface using molecular-dynamics computer simulations. The empirical valence bond approach is used to couple two diabatic states, covalent and ionic, in the electronically adiabatic limit. Umbrella sampling calculations are used to calculate the potential of mean force along the reaction coordinate (defined as the t-Bu to Cl distance) in bulk water and in several locations at the interface. We find a significant increase of the dissociation barrier height and of the reaction free energy at the interface relative to the bulk. This is shown to be due to the reduced polarity of the interface. Reactive flux correlation function calculations show significant deviation of the rate constant from the transition-state theory: The transmission coefficients range from 0.49 in the bulk to 0.05 above the Gibbs surface. The low transmission coefficient at the interface despite the lower friction is shown to be due to slow vibrational relaxation.

The ionic dissociation step of the nucleophilic substitution reaction t-BuCl --> t-Bu(+) + Cl(-) is studied at the water/carbon tetrachloride interface using molecular dynamics computer simulations. The empirical valence bond approach is used to couple two diabatic states, covalent and ionic, in the electronically adiabatic limit. The umbrella sampling technique is used to calculate the potential of mean force along the reaction coordinate (defined as the t-Bu to Cl distance) at several interface regions of varying distances from the Gibbs dividing surface. We find a significant increase of the ionic dissociation barrier height and of the reaction free energy at the interface relative to bulk water. This is shown to be due to the reduced polarity of the interface which causes a destabilization of the pure ionic state. However, deformation to the neat interface structure in the form of water protrusions into the organic phase may provide partial stabilization of the ionic species. The importance of these structural effects is examined by repeating the calculations with an artificially smooth interface. The destabilization of the ionic state at the interface also manifests itself with a rapid (picosecond time scale) recombination dynamics of the ions to form the parent molecule followed by a slow vibrational relaxation.