A harmonic transition state approximation for the duration of reactive events in complex molecular rearrangements

被引:94
作者
Chaudhury, Srabanti [1 ]
Makarov, Dmitrii E.
机构
[1] Univ Texas Austin, Dept Chem & Biochem, Austin, TX 78712 USA
基金
美国国家科学基金会;
关键词
FINDING SADDLE-POINTS; POLYMER TRANSLOCATION; PROTEIN TRANSLOCATION; COMPUTER-SIMULATIONS; FORCE SPECTROSCOPY; TRAJECTORIES; NANOPORE; PATHS; TIME; MECHANICS;
D O I
10.1063/1.3459058
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
Motivated by recent experimental efforts to measure the time a molecular system spends in transit between the reactants and the products of a chemical reaction, here we study the properties of the distribution of such transit times for the case of conservative dynamics on a multidimensional energy landscape. Unlike reaction rates, transit times are not invariant with respect to the order parameter (a.k.a. the experimental signal) used to monitor the progress of a chemical reaction. Nevertheless, such order parameter dependence turns out to be relatively weak. Moreover, for several model systems we find that the probability distribution of transit times can be estimated analytically, with reasonable accuracy, by assuming that the order parameter coincides with the direction of the unstable normal mode at the transition state. Although this approximation tends to overestimate the actual mean transit time measured using other order parameters, it yields asymptotically correct long-time behavior of the transit time distribution, which is independent of the order parameter. (C) 2010 American Institute of Physics. [doi:10.1063/1.3459058]
引用
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页数:11
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