Theoretical and Computational Chemistry

Quantum versus Classical Unimolecular Fragmentation Rate Constants and Activation Energies at Finite Temperature from Direct Dynamics Simulations

Authors

Abstract

In the present work, we investigate how nuclear quantum effects modify the temperature dependent rate constants and, consequently, the activation energies in unimolecular reactions. In the reactions under study, nuclear quantum effects mainly stem from the presence of a large zero point energy. Thus, we investigate the behavior of methods compatible with direct dynamics simulations, the Quantum Thermal Bath (QTB) and Ring Polymer Molecular Dynamics (RPMD). To this end, we first compare them with quantum reaction theory for a model Morse potential before extending this comparison to molecular models. Our results show that, in particular in the temperature range comparable with or lower than the zero point energy of the system, the RPMD method is able to correctly catch the classical-quantum difference. {On the other hand, although the QTB provides a good description of equilibrium properties including zero-point energy effects, it} largely overestimates the rate constants. The origin of the different behaviours is in the different distance distributions provided by the two methods and in particular how they differently describe the tails of such distributions.

Content

Thumbnail image of RPMD_Unimol_Frag_rev1.pdf

Supplementary material

Thumbnail image of RPMD_Unimol_Frag_SI.pdf
Quantum versus Classical Unimolecular Fragmentation Rate Constants and Activation Energies at Finite Temperature from Direct Dynamics Simulations
In the supporting information we report: (i) details of the algorithm used to propagete RPMD trajectories; (ii) temperature correlation function at different friction values; (iii) further details on life-times and rate constants.