Coupled Anharmonic Thermochemistry from Stratified Monte Carlo Integration

This study presents configuration integral Monte Carlo integration (CIMCI), a new semiclassical method for handling fully coupled anharmonicity in gas-phase thermodynamics that promises to be black boxable, to be applicable to all kinds of anharmonicity, and to scale better at higher dimensionality than other methods for handling gas-phase molecular anharmonicity. The method does so using automatically and recursively stratified, simultaneous Monte Carlo (MC) integration of multiple functions, following a modified version of the standard MISER scheme that converges at a rate of about the square of naive MC integration. For the small systems analyzed by this study where proper reference data is available (H2O and H2O2), the method's anharmonic entropy corrections match reference data better than those of other black box anharmonic methods, e.g., vibrational perturbation theory (VPT2) and the McClurg hindered rotor model used with automatic detection of rotors; for H2O2 and NH2OH, the method is also in general agreement with one-dimensional hindered rotor treatments at low temperatures. This holds even when sampling with CIMCI is done with primitive force fields, e.g., UFF, while the competing methods are used with proper, comprehensive potentials, e.g., the M06-2X metahybrid density-functional theory (DFT) functional.

Automated summary

This study introduces a new semiclassical method called configuration integral Monte Carlo integration (CIMCI) for handling fully coupled anharmonicity in gas-phase thermodynamics. It promises to be black boxable, applicable to all kinds of anharmonicity, and to scale better at higher dimensionality compared to other methods. The method uses simultaneous Monte Carlo integration of multiple functions and shows better agreement with reference data for anharmonic entropy corrections in small systems like H2O and H2O2.