Theoretical study on the solvent effect of the nitrosyl cation (NO ~+) generating reaction

摘要

Nitrosyl cation (NO~+) generating reaction HONO ~+ H+ → NO~+ + H_2O has been theoretically investigated by B3LYP and high-electron-correlation QCISD methods with 6-31G (d,p) basis set. The solvent effects on the geometries, reaction path properties, energies, thermodynamic, and kinetic characters in four solvents (benzene, tetrahydrofuran, acetonitrile, and water) have been calculated using self-consistent reaction field (SCRF) approach with the polarizable continuum model (PCM). The results show that the activation energy barriers and the relative energies of the products are decreased with increase of the polarities of the solvents, and the reaction is favored in polar solvents thermodynamically and kinetically.