English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

We consider a proton-transfer (PT) system described by a proton-transferreaction (PTR) coordinate and a rate promoting vibrational (RPV) coordinateinteracting with a non-Markovian heat-bath. While dynamics of PT processes hasbeen widely discussed using two-dimensional (2D) potential energy surfaces(PES), the role of the heat-bath, in particular, for a realistic form of thesystem-bath interaction has not been well explored. Previous studies arelargely based on one-dimensional model and linear-linear (LL) system-bathinteraction. In the present study, we introduce an exponential-linear (EL)system-bath interaction, which is derived from the analysis of a PTR-PRV systemin a realistic situation. This interaction mainly causes vibrational dephasingin the PTR mode and population relaxation in the RPV mode. Numericalsimulations were carried out using hierarchy equations of motion approach. Weanalyze the role of the heat-bath interaction on the chemical reaction rate asa function of the system-bath coupling strength at different temperature andfor different values of the bath correlation time. A prominent feature of thepresent result is that while the reaction rate predicted from classical andquantum Kramers theory increases as the temperature increases, the present ELinteraction model exhibits opposite temperature dependence. Kramers turn-overprofile of the reaction rate as a function of the system-bath coupling is alsosuppressed in the present EL model turning into a plateau-like curve for largersystem-bath interaction strength. Such features arise from the interplay of thevibrational dephasing process in the PTR mode and the population relaxationprocess in the RPV mode.

Proton Tunneling in a Two-Dimensional Potential Energy Surface with a Non-linear System-Bath Interaction: Thermal Suppression of Reaction Rate