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Kinetic isotope effect (KIE) is a common physicochemical effect to elucidate complicated microscopic reaction mechanism in biological, chemical and physical systems. Especially, the exchange of hydrogen to deuterium is a standard approach…

化学物理 · 物理学 2019-08-16 Ken Sakaushi

A general method for computing kinetic isotope effects is described. The method uses the quantum-instanton approximation and is based on the thermodynamic integration with respect to the mass of the isotopes and on the path-integral…

化学物理 · 物理学 2007-05-23 Jiri Vanicek , William H. Miller

The shift in chemical equilibria due to isotope substitution is often exploited to gain insight into a wide variety of chemical and physical processes. It is a purely quantum mechanical effect, which can be computed exactly using…

统计力学 · 物理学 2014-07-04 Michele Ceriotti , Thomas E. Markland

Temperature dependence of the thermal rate constants and kinetic isotope effects (KIE) of the CN + C2H6 gas-phase hydrogen abstraction reaction was theoretically determined within the 25-1000 K temperature range, i.e., from ultra-low to…

化学物理 · 物理学 2024-03-05 Joaquin Espinosa-Garcia , Somnath Bhowmick

It is shown here that the Exact Exchange (EE) formalism provides a natural and rigorous approach for a Density Functional Theory (DFT) of the Integer Quantum Hall Effect (IQHE). Application of a novel EE method to a quasi two-dimensional…

介观与纳米尺度物理 · 物理学 2017-12-06 D. Miravet , G. J. Ferreira , C. R. Proetto

We investigate the quantum-mechanical localization of protonated and deterated isotopes in the symmetric low-barrier hydrogen-bonds of potassium dihydrogen phosphate (KDP) crystals in the paraelectric phase. The spatial density…

材料科学 · 物理学 2010-02-09 Varadharajan Srinivasan , Roberto Car , Daniel Sebastiani

The previously developed technique for evaluation of charge-transfer and electron-excitation processes in low-energy heavy-ion collisions [I.I. Tupitsyn et al., Phys. Rev. A 82, 042701(2010)] is extended to collisions of ions with neutral…

A kinetic theory model is developed for positron-impact ionization (PII) with neutral, rarefied gases. Particular attention is given to the sharing of available energy between the post-ionization constituents. A simple model for the…

等离子体物理 · 物理学 2016-03-02 G. J. Boyle , W. J. Tattersall , D. G. Cocks , S. Dujko , R. D. White

When two phases of water are at equilibrium, the ratio of hydrogen isotopes in each is slightly altered due to their different phase affinities. This isotopic fractionation process can be utilized to analyze water's movement in the world's…

化学物理 · 物理学 2013-07-30 Thomas E. Markland , B. J. Berne

The kinetic compensation effect (KCE), observed in many fields of science, is the systematic variation in the apparent magnitudes of the Arrhenius parameters $E_a$, the energy of activation, and $\nu$, the preexponential factor, as a…

统计力学 · 物理学 2018-10-03 Nayeli Zuniga-Hansen , Leonardo E. Silbert , M. Mercedes Calbi

Path integral implementation of the quantum instanton approximation currently belongs among the most accurate methods for computing quantum rate constants and kinetic isotope effects, but its use has been limited due to the rather high…

化学物理 · 物理学 2017-05-10 Konstantin Karandashev , Jiri Vanicek

For the theoretical understanding of the reactivity of complex chemical systems accurate relative energies between intermediates and transition states are required. Despite its popularity, density functional theory (DFT) often fails to…

化学物理 · 物理学 2016-06-23 Gregor N. Simm , Markus Reiher

Detailed comparisons between theory and experiment for quantum electrodynamics (QED) effects in He-like ions have been performed in the literature to search for hints of new physics. Different frequentist statistical analyses of the…

Flow-based generative models can be viewed through a physics lens: sampling transports a particle from noise to data by integrating a time-varying velocity field, and each sample corresponds to a trajectory with its own dynamical effort.…

机器学习 · 计算机科学 2026-02-10 Ziyun Li , Huancheng Hu , Soon Hoe Lim , Xuyu Li , Fei Gao , Enmao Diao , Zezhen Ding , Michalis Vazirgiannis , Henrik Bostrom

Introducing a new vertex function, Z(E), of an energy variable E, we derive a new equation for the effective interaction. The equation is obtained by replacing the Q-box in the Krenciglowa-Kuo (KK) method by Z(E). This new approach can be…

核理论 · 物理学 2011-02-22 K. Suzuki , R. Okamoto , H. Kumagai , S. Fujii

A new density functional theory (DFT) exchange-correlation functional for the exploration of reaction mechanisms is proposed. This new functional, denoted BMK (Boese-Martin for Kinetics), has an accuracy in the 2 kcal/mol range for…

化学物理 · 物理学 2007-05-23 A. Daniel Boese , Jan M. L. Martin

The isotope effect in the melting temperature of ice Ih has been studied by free energy calculations within the path integral formulation of statistical mechanics. Free energy differences between isotopes are related to the dependence of…

材料科学 · 物理学 2011-08-19 R. Ramirez , C. P. Herrero

This work presents a multifaceted experimental study of collisions of Na$^{+}$ and K$^{+}$ ions in the energy range 0.5 -- 10 keV with He and Ar atoms. Absolute cross sections for charge-exchange, ionization, stripping and excitation were…

原子物理 · 物理学 2015-08-26 R. A. Lomsadze , M. R. Gochitashvili , N. O. Mosulishvili , R. Ya. Kezerashvili

We calculated reaction rate constants including atom tunneling for the hydrogen abstraction reaction CH3OH+H -> CH2OH+H2 with the instanton method. The potential energy was fitted by a neural network, that was trained to…

化学物理 · 物理学 2020-09-10 April. M. Cooper , Johannes Kästner

The nuclear-electronic orbital (NEO) method is a well-established approach for treating nuclei quantum mechanically in molecular systems beyond the usual Born-Oppenheimer approximation. In this work, we present a strategy to implement the…

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