作者: Bingqing Cheng , Michele Ceriotti
DOI: 10.1063/1.4904293
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摘要: Fractionation of isotopes among distinct molecules or phases is a quantum effect which often exploited to obtain insights on reaction mechanisms, biochemical, geochemical, and atmospheric phenomena. Accurate evaluation isotope ratios in atomistic simulations challenging, because one needs perform thermodynamic integration with respect the mass, along time-consuming path integral calculations. By re-formulating problem as particle exchange ring polymer partition function, we derive new estimators giving direct access differential partitioning isotopes, can simplify calculations by avoiding integration. We demonstrate efficiency these applying them investigate fractionation gas-phase Zundel cation, few simple hydrocarbons.