An alternative derivation of ring-polymer molecular dynamics transition-state theory

被引:13
|
作者
Hele, Timothy J. H. [1 ,2 ]
Althorpe, Stuart C. [1 ]
机构
[1] Univ Cambridge, Dept Chem, Lensfield Rd, Cambridge CB2 1EW, England
[2] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14853 USA
关键词
CHEMICAL-REACTION RATES; RATE CONSTANTS; QUANTUM; MECHANICS;
D O I
10.1063/1.4947589
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In a previous article [T. J. H. Hele and S. C. Althorpe, J. Chem. Phys. 138, 084108 (2013)], we showed that the t -> 0(+) limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the t -> 0(+) limit of a new type of quantum flux-side time-correlation function, in which the dividing surfaces are invariant to imaginary-time translation; in other words, that RPMD transition-state theory (RMPD-TST) is a t -> 0(+) quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum t -> 0(+) limit and claimed that it gives instead the centroid-density approximation. Here we show that the t -> 0(+) limit derived by Jang and Voth is in fact RPMD-TST. Published by AIP Publishing.
引用
收藏
页数:4
相关论文
共 50 条
  • [31] Isotopic separation of helium through graphyne membranes: a ring polymer molecular dynamics study
    Bhowmick, Somnath
    Hernandez, Marta I.
    Campos-Martinez, Jose
    Suleimanov, Yury V.
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2021, 23 (34) : 18547 - 18557
  • [32] Caracal: A Versatile Ring Polymer Molecular Dynamics Simulation Package
    Steffen, Julien
    JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2023, 19 (16) : 5334 - 5355
  • [33] Ring-Polymer Molecular Dynamics for the Prediction of Low-Temperature Rates: An Investigation of the C(1D) + H2 Reaction
    Hickson, Kevin M.
    Loison, Jean-Christophe
    Guo, Hua
    Suleimanov, Yury V.
    JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2015, 6 (21): : 4194 - 4199
  • [34] Ring polymer molecular dynamics with surface hopping
    Shushkov, Philip
    Li, Richard
    Tully, John C.
    JOURNAL OF CHEMICAL PHYSICS, 2012, 137 (22)
  • [35] Ring Polymer Molecular Dynamics with Electronic Transitions
    Zhao, Ruji
    You, Peiwei
    Meng, Sheng
    PHYSICAL REVIEW LETTERS, 2023, 130 (16)
  • [36] Ring-polymer molecular dynamical calculations for the F plus HCl → HF plus Cl reaction on the ground 12A′ potential energy surface
    Bai, Mengna
    Lu, Dandan
    Li, Yongle
    Li, Jun
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2016, 18 (47) : 32031 - 32041
  • [37] Transition-State Theory, Dynamics, and Narrow Time Scale Separation in the Rate-Promoting Vibrations Model of Enzyme Catalysis
    Peters, Baron
    JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2010, 6 (05) : 1447 - 1454
  • [38] Nuclear quantum effects in state-selective scattering from ring polymer molecular dynamics
    Marjollet, Adrien
    Welsch, Ralph
    JOURNAL OF CHEMICAL PHYSICS, 2020, 152 (19)
  • [39] Derivation of a true (t → 0+) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing
    Althorpe, Stuart C.
    Hele, Timothy J. H.
    JOURNAL OF CHEMICAL PHYSICS, 2013, 139 (08)
  • [40] Ring-polymer Molecular Dynamics Simulation for the Adsorption of H2 on Ice Clusters (H2O)n (n=8, 10, and 12)
    Murakami, Tatsuhiro
    Ogino, Kanon
    Hashimoto, Yu
    Takayanagi, Toshiyuki
    CHEMPHYSCHEM, 2023, 24 (10)