Polyrate 2023: A computer program for the calculation of chemical reaction rates for polyatomics. New version announcement

Abstract

Polyrate is a suite of computer programs for the calculation of chemical reaction rates of polyatomic species (including atoms and diatoms as special cases) by variational transition state theory (VTST); conventional transition state theory is also supported. Polyrate can calculate the rate constants for both bimolecular reactions and unimolecular reactions, and it can be applied to reactions in the gas phase, liquid solution phase, or solid state and to reactions at gas–solid interfaces. Polyrate can perform VTST calculations on gas-phase reactions with both tight and loose transition states. For tight transition states it uses the reaction-path (RP) variational transition state theory developed by Garrett and Truhlar, and for loose transition states it uses variable-reaction-coordinate (VRC) variational transition state theory developed by Georgievskii and Klippenstein. The RP methods used for tight transition states are conventional transition state theory, canonical variational transition state theory (CVT), and microcanonical variational transition state theory (μVT) with multidimensional semiclassical approximations for tunneling and nonclassical reflection. For VRC calculations, rate constants may be calculated for canonical or microcanonical ensembles or energy- and total-angular-momentum resolved microcanonical ensembles. Pressure-dependent rate constants for elementary reactions can be computed using system-specific quantum RRK theory (SS-QRRK) with the information obtained from high-pressure-limit VTST calculation as input by using the SS-QRRK utility code. Alternatively, Polyrate 2023 may be interfaced with TUMME 2023 for a master-equation treatment of pressure dependence or to obtain phenomenological rate constants for complex mechanisms. Potential energy surfaces may be analytic functions evaluated by subroutines, or they may be implicit surfaces defined by electronic structure input files or interface subroutines containing energies, gradients, and force constants (Hessians). For the latter, Polyrate can be used in conjunction with various interfaces to electronic structure programs for direct dynamics, and it has routines designed to make such interfacing straightforward. Polyrate supports six options for direct dynamics, namely (i) straight single-level direct dynamics, (ii) zero-order interpolated variational transition state theory (IVTST-0), (iii) first-order interpolated variational transition state theory (IVTST-1), (iv) interpolated variational transition state theory by mapping (IVTST-M), (v) variational transition state theory with interpolated single-point energies (VTST-ISPE), and (vi) variational transition state theory with interpolated optimized corrections (VTST-IOC). Polyrate can handle multistructural and torsional-potential anharmonicity in conjunction with the MSTor program. Polyrate 2023 contains 112 test runs, and 46 of these are for direct dynamics calculations; 85 of the test runs are single-level runs, and 27 are dual-level calculations.