Accelerating equilibrium isotope effect calculations. I. Stochastic thermodynamic integration with respect to mass

Accurate path integral Monte Carlo or molecular dynamics calculations of isotope effects have until recently been expensive because of the necessity to reduce three types of errors present in such calculations: statistical errors due to sampling, path integral discretization errors, and thermodynamic integration errors. While the statistical errors can be reduced with virial estimators and path integral discretization errors with high-order factorization of the Boltzmann operator, here we propose a method for accelerating isotope effect calculations by eliminating the integration error. We show that the integration error can be removed entirely by changing particle masses stochastically during the calculation and by using a piecewise linear umbrella biasing potential. Moreover, we demonstrate numerically that this approach does not increase the statistical error. The resulting acceleration of isotope effect calculations is demonstrated on a model harmonic system and on deuterated species of methane.

Accelerating path integral evaluation of equilibrium and kinetic isotope effects

Konstantin Karandashev

Investigating the effect of isotope substitution on equilibrium and kinetic properties of molecules has become an important tool for estimating the importance of nuclear quantum effects. In this work, we discuss calculating both equilibrium and kinetic isotope effects, i.e., the isotope effects on a system's partition function and a reaction's rate constant. With the help of Feynman's path integral formalism, both quantities can be estimated using standard Monte Carlo methods that scale favorably with system's dimensionality; improving efficiency of such approaches is the main focus of this work. First of all, we developed a novel procedure for changing mass stochastically during an equilibrium isotope effect calculation, and evaluated the numerical benefits of combining it with two popular approaches for calculating isotope effects, using either direct estimators or thermodynamic integration. We demonstrate that the modification improves statistical convergence of both methods, and that it additionally allows to eliminate integration error of thermodynamic integration. The improved methods are tested on equilibrium isotope effects in a model harmonic system and in methane. Then we turn our attention to kinetic isotope effect calculations with the quantum instanton approximation, a method whose path integral implementation belongs among the most accurate approaches for evaluating reaction rate constants in polyatomic systems. To accelerate quantum instanton calculations of kinetic isotope effects, we combine higher-order Boltzmann operator factorization with virial estimators, allowing us to speed up both the convergence to the quantum limit and statistical convergence of the calculation. We estimate the overall resulting acceleration using H+H2/D+D2 as a benchmark system, and then apply the accelerated method to several kinetic isotope effects associated with the H+CH4=H2+CH3 exchange. Last but not least, we explored ways to improve on the quantum instanton approximation for reaction rate constants. To that end, we review quantum instanton and Hansen-Andersen approximations, and propose a combined method, which, as the Hansen-Andersen approximation, has the correct high-temperature behavior, and at the same time, as the quantum instanton approximation, has more flexibility by allowing the dividing surface for the reaction to split into two surfaces at low temperatures. The properties of the combined method are tested on symmetric and asymmetric Eckart barrier.

EPFL2018

Quantum-instanton evaluation of the kinetic isotope effects

Jiri Vanicek

A general quantum-mechanical method for computing kinetic isotope effects is presented. The method is based on the quantum-instanton approximation for the rate constant and on the path-integral Metropolis–Monte Carlo evaluation of the Boltzmann operator matrix elements. It computes the kinetic isotope effect directly, using a thermodynamic integration with respect to the mass of the isotope, thus avoiding the more computationally expensive process of computing the individual rate constants. The method should be more accurate than variational transition-state theories or the semiclassical instanton method since it does not assume a single tunneling path and does not use a semiclassical approximation of the Boltzmann operator. While the general Monte Carlo implementation makes the method accessible to systems with a large number of atoms, we present numerical results for the Eckart barrier and for the collinear and full three-dimensional isotope variants of the hydrogen exchange reaction H+H2H2+H. In all seven test cases, for temperatures between 250 and 600 K, the error of the quantum instanton approximation for the kinetic isotope effects is less than ~10%.

2005

Accelerating path integral evaluation of equilibrium and kinetic isotope effects

Konstantin Karandashev

EPFL2018