Anharmonic Densities of States for Vibrationally Excited I-(H2O), (H2O)(2), and I-(H2O)(2)

作者：Ma Xinyou; Yang Nan; Johnson Mark A; Hase William L^*

来源：Journal of Chemical Theory and Computation, 2018, 14(8): 3986-3997.

DOI：10.1021/acs.jctc.8b00300

Monte Carlo sampling calculations were performed to determine the anharmonic sum of states, N-anh( E), for I-(H2O), (H2O)(2), and I-(H2O)(2) versus internal energy up to their dissociation energies. The anharmonic density of states, rho(anh)(E), is found from the energy derivative of N-anh(E). Analytic potential energy functions are used for the calculations, consisting of TIP4P for H2O center dot center dot center dot H2O interactions and an accurate two-body potential for the I-center dot center dot center dot H2O fit to quantum chemical calculations. The extensive Monte Carlo samplings are computationally demanding, and the use of computationally efficient potentials was essential for the calculations. Particular emphasis is directed toward I-(H2O)(2), and distributions of its structures versus internal energy are consistent with experimental studies of the temperature-dependent vibrational spectra. At their dissociation thresholds, the anharmonic to harmonic density of states ratio, rho(anh)(E)/rho(h)(E), is similar to 2, similar to 3, and similar to 260 for I-(H2O), (H2O)(2), and I-(H2O)(2), respectively. The large ratio for I-(H2O)(2) results from the I-(H2O)(2) -> I-(H2O) + H2O dissociation energy being more than 2 times larger than the (H2O)(2) -> 2H(2)O dissociation energy, giving rise to highly mobile H2O molecules near the I-(H2O)(2) dissociation threshold. This work illustrates the importance of treating anharmonicity correctly in unimolecular rate constant calculations.

• 出版日期2018-8