Literature DB >> 21428604

On the equivalence of two commonly used forms of semiclassical instanton theory.

Stuart C Althorpe1.   

Abstract

Semiclassical instanton theory gives an approximate description of deep tunneling by means of periodic orbits on the inverted potential energy surface. There are two versions of the theory, one derived by taking a semiclassical limit of the exact flux-side time-correlation function and the other by starting from the "Im F" premise, in which the partition function is analytically continued into the complex plane. Here, we provide a derivation showing that the two versions of the theory are exactly equivalent. Unlike a previous derivation (which was restricted to a system-bath model), our derivation is completely general, and thus establishes that the "Im F" premise, which is behind such methods as quantum transition-state theory and ring polymer molecular dynamics rate-theory, is correct in the steepest-descent limit.

Entities:  

Year:  2011        PMID: 21428604     DOI: 10.1063/1.3563045

Source DB:  PubMed          Journal:  J Chem Phys        ISSN: 0021-9606            Impact factor:   3.488


  5 in total

Review 1.  Kinetic isotope effects and how to describe them.

Authors:  Konstantin Karandashev; Zhen-Hao Xu; Markus Meuwly; Jiří Vaníček; Jeremy O Richardson
Journal:  Struct Dyn       Date:  2017-12-13       Impact factor: 2.920

2.  Atom tunnelling in the reaction NH3+ + H2 → NH4+ + H and its astrochemical relevance.

Authors:  Sonia Álvarez-Barcia; Marie-Sophie Russ; Jan Meisner; Johannes Kästner
Journal:  Faraday Discuss       Date:  2016-12-22       Impact factor: 4.008

3.  Formation of the prebiotic molecule NH2CHO on astronomical amorphous solid water surfaces: accurate tunneling rate calculations.

Authors:  Lei Song; Johannes Kästner
Journal:  Phys Chem Chem Phys       Date:  2016-10-26       Impact factor: 3.676

4.  Quantum tunneling during interstellar surface-catalyzed formation of water: the reaction H + H2O2 → H2O + OH.

Authors:  Thanja Lamberts; Pradipta Kumar Samanta; Andreas Köhn; Johannes Kästner
Journal:  Phys Chem Chem Phys       Date:  2016-12-07       Impact factor: 3.676

5.  Instanton theory for Fermi's golden rule and beyond.

Authors:  Imaad M Ansari; Eric R Heller; George Trenins; Jeremy O Richardson
Journal:  Philos Trans A Math Phys Eng Sci       Date:  2022-03-28       Impact factor: 4.226

  5 in total

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