FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2081997945> ?p ?o ?g. }

• W2081997945 abstract "The coupled transfer of electrons and protons is a central feature of biological and molecular catalysis, yet fundamental aspects of these reactions remain poorly understood. In this study, we extend the ring polymer molecular dynamics (RPMD) method to enable direct simulation of proton-coupled electron transfer (PCET) reactions across a wide range of physically relevant regimes. In a system-bath model for symmetric, co-linear PCET in the condensed phase, RPMD trajectories reveal distinct kinetic pathways associated with sequential and concerted PCET reaction mechanisms, and it is demonstrated that concerted PCET proceeds by a solvent-gating mechanism in which the reorganization energy is mitigated by charge cancellation among the transferring particles. We further employ RPMD to study the kinetics and mechanistic features of concerted PCET reactions across multiple coupling regimes, including the fully non-adiabatic (both electronically and vibrationally non-adiabatic), partially adiabatic (electronically adiabatic, but vibrationally non-adiabatic), and fully adiabatic (both electronically and vibrationally adiabatic) limits. Comparison of RPMD with the results of PCET rate theories demonstrates the applicability of the direct simulation method over a broad range of conditions; it is particularly notable that RPMD accurately predicts the crossover in the thermal reaction rates between different coupling regimes while avoiding a priori assumptions about the PCET reaction mechanism. Finally, by utilizing the connections between RPMD rate theory and semiclassical instanton theory, we show that analysis of ring-polymer configurations in the RPMD transition path ensemble enables the a posteriori determination of the coupling regime for the PCET reaction. This analysis reveals an intriguing and distinct “transient-proton-bridge” mechanism for concerted PCET that emerges in the transition between the proton-mediated electron superexchange mechanism for fully non-adiabatic PCET and the hydrogen atom transfer mechanism for partially adiabatic PCET. Taken together, these results provide a unifying picture of the mechanisms and physical driving forces that govern PCET across a wide range of physical regimes, and they raise the possibility for PCET mechanisms that have not been previously reported." @default.
• W2081997945 created "2016-06-24" @default.
• W2081997945 creator A5004444057 @default.
• W2081997945 creator A5028949819 @default.
• W2081997945 date "2013-04-02" @default.
• W2081997945 modified "2023-10-11" @default.
• W2081997945 title "Direct simulation of proton-coupled electron transfer across multiple regimes" @default.
• W2081997945 cites W1965005651 @default.
• W2081997945 cites W1966702069 @default.
• W2081997945 cites W1966723131 @default.
• W2081997945 cites W1968963012 @default.
• W2081997945 cites W1970327813 @default.
• W2081997945 cites W1972279780 @default.
• W2081997945 cites W1973127667 @default.
• W2081997945 cites W1974457621 @default.
• W2081997945 cites W1976945994 @default.
• W2081997945 cites W1977482735 @default.
• W2081997945 cites W1978936677 @default.
• W2081997945 cites W1979112715 @default.
• W2081997945 cites W1982265377 @default.
• W2081997945 cites W1984135072 @default.
• W2081997945 cites W1986670180 @default.
• W2081997945 cites W1988936907 @default.
• W2081997945 cites W1990551042 @default.
• W2081997945 cites W1993439357 @default.
• W2081997945 cites W1994188548 @default.
• W2081997945 cites W1995842593 @default.
• W2081997945 cites W1996435744 @default.
• W2081997945 cites W1998904893 @default.
• W2081997945 cites W2002265279 @default.
• W2081997945 cites W2003196873 @default.
• W2081997945 cites W2007933544 @default.
• W2081997945 cites W2009189790 @default.
• W2081997945 cites W2009902266 @default.
• W2081997945 cites W2017158178 @default.
• W2081997945 cites W2019012502 @default.
• W2081997945 cites W2022231452 @default.
• W2081997945 cites W2025029409 @default.
• W2081997945 cites W2025504048 @default.
• W2081997945 cites W2027743806 @default.
• W2081997945 cites W2027958666 @default.
• W2081997945 cites W2031843459 @default.
• W2081997945 cites W2031904472 @default.
• W2081997945 cites W2032224966 @default.
• W2081997945 cites W2037709521 @default.
• W2081997945 cites W2040396113 @default.
• W2081997945 cites W2041272682 @default.
• W2081997945 cites W2041753261 @default.
• W2081997945 cites W2041930594 @default.
• W2081997945 cites W2042951945 @default.
• W2081997945 cites W2046205244 @default.
• W2081997945 cites W2047224922 @default.
• W2081997945 cites W2049738344 @default.
• W2081997945 cites W2051402020 @default.
• W2081997945 cites W2052932598 @default.
• W2081997945 cites W2053602288 @default.
• W2081997945 cites W2056272477 @default.
• W2081997945 cites W2057379537 @default.
• W2081997945 cites W2057980421 @default.
• W2081997945 cites W2058604300 @default.
• W2081997945 cites W2059280007 @default.
• W2081997945 cites W2059844062 @default.
• W2081997945 cites W2062328965 @default.
• W2081997945 cites W2063170749 @default.
• W2081997945 cites W2063262828 @default.
• W2081997945 cites W2068524453 @default.
• W2081997945 cites W2068920655 @default.
• W2081997945 cites W2069259235 @default.
• W2081997945 cites W2069395328 @default.
• W2081997945 cites W2073006389 @default.
• W2081997945 cites W2074768610 @default.
• W2081997945 cites W2074839964 @default.
• W2081997945 cites W2075552235 @default.
• W2081997945 cites W2076066188 @default.
• W2081997945 cites W2076968034 @default.
• W2081997945 cites W2079167667 @default.
• W2081997945 cites W2080706419 @default.
• W2081997945 cites W2080889138 @default.
• W2081997945 cites W2083192780 @default.
• W2081997945 cites W2085022730 @default.
• W2081997945 cites W2088236433 @default.
• W2081997945 cites W2088436475 @default.
• W2081997945 cites W2091237955 @default.
• W2081997945 cites W2091983181 @default.
• W2081997945 cites W2093115355 @default.
• W2081997945 cites W2094742025 @default.
• W2081997945 cites W2095154453 @default.
• W2081997945 cites W2099490136 @default.
• W2081997945 cites W2103794950 @default.
• W2081997945 cites W2105348198 @default.
• W2081997945 cites W2105533397 @default.
• W2081997945 cites W2112154906 @default.
• W2081997945 cites W2112940941 @default.
• W2081997945 cites W2118159170 @default.
• W2081997945 cites W2118479650 @default.
• W2081997945 cites W2124129640 @default.
• W2081997945 cites W2126916397 @default.
• W2081997945 cites W2142244352 @default.
• W2081997945 cites W2157256442 @default.
• W2081997945 cites W2161929344 @default.

• next