Locating the lowest free-energy point on conical intersection in polar solvent: reference interaction site model self-consistent field study of ethylene and CH2NH2(+).

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摘要：

We present a theoretical method for locating the lowest free-energy points on conical intersections (CIs) in solution using the reference interaction site model self-consistent field (RISM-SCF) theory. Based on the linear-response theory, the nonequilibrium free energy is defined as a quadratic function of solvation coordinates, the parameters in which are directly obtained byab initioRISM-SCF calculations. This free energy is easily incorporated into an efficient CI optimization procedure in gas phase. The present method is applied to thecis-transphotoisomerizations of ethylene and methaniminium cation(CH2NH2+)in polar solvents. We show that the geometries and energies of CIs are largely affected by the solute-solvent electrostatic interaction. In particular, the hydrogen migration of ethylene observed at CIs in the gas phase disappears in protic solvents due to the large stabilization of the zwitterionic state.

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Foreign trade regulation

DOI：

10.1063/1.2038867

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年份：

2005