Monte Carlo evaluation of the equilibrium isotope effects using the Takahashi-Imada factorization of the Feynman path integral

The Feynman path integral approach for computing equilibrium isotope effects and isotope fractionation corrects the approximations made in standard methods, although at significantly increased computational cost. We describe an accelerated path integral approach based on three ingredients: the fourth- order Takahashi-Imada factorization of the path integral, thermodynamic integration with respect to mass, and centroid virial estimators for relevant free energy derivatives. While the frst ingredient speeds up convergence to the quantum limit, the second and third improve statistical convergence. The combined method is applied to compute the equilibrium constants for isotope exchange reactions H2+D=H+HD and H2+D2=2HD

Direct evaluation of the temperature dependence of the rate constant based on the quantum instanton approximation

A general method for the direct evaluation of the temperature dependence of the quantum-mechanical reaction rate constant in many-dimensional systems is described. The method is based on the quantum instanton approximation for the rate constant, thermodynamic integration with respect to the inverse temperature, and the path integral Monte Carlo evaluation. It can describe deviations from the Arrhenius law due to the coupling of rotations and vibrations, zero-point energy, tunneling, corner-cutting, and other nuclear quantum effects. The method is tested on the Eckart barrier and the full-dimensional H+H2→H2+H reaction. In the temperature range from 300 to 1500 K, the error of the present method remains within 13% despite the very large deviations from the Arrhenius law. The direct approach makes the calculations much more efficient, and the efficiency is increased even further (by up to two orders of magnitude in the studied reactions) by using optimal estimators for reactant and transition state thermal energies. Which of the estimators is optimal, however, depends on the system and the strength of constraint in a constrained simulation

On the Complementarity of the Harmonic Oscillator Model and the Classical Wigner–Kirkwood Corrected Partition Functions of Diatomic Molecules

The vibrational and rovibrational partition functions of diatomic molecules are considered in the regime of intermediate temperatures. The low temperatures are those at which the harmonic oscillator approximation is appropriate, and the high temperatures are those at which classical partition function (with Wigner–Kirkwood correction) is applicable. The complementarity of the harmonic oscillator and classical integration over the phase space approaches is investigated for the CO and H2+ molecules showing that those two approaches are complementary in the sense that they smoothly overlap