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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Quantum Rate Constants from Short-Time Dynamics: An Analytic Continuation Approach
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Quantum Rate Constants from Short-Time Dynamics: An Analytic Continuation Approach

机译:短时动力学中的量子速率常数:一种解析连续方法

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摘要

A method for calculating the quantum canonical rate constant of chemical reactions in a many body system by means of a short-time flux autocorreltion function combined with a maximum entropy numerical analytic continuation scheme is presented. The rate constant is expressed as the time integral of the real-time flux autocorreltion function. The real-time flux autocorrelation function is evaluated for short times fully quantum mechanically by path integral Monte Carlo simulations. The maximum entropy approach is then used to extract the rate from the short real-time fux autocorreltion data. We present two numerical tests, one for proton transfer in harmoic dissipative environments in the photosynthetic reaction center. The results obtained using the flux autocorreltion data up to the time of no more than #beta#h are in excellent agreement with the eact quantum calculation over a wide range of parameters including even the tunneling regime.
机译:提出了一种基于短时通量自相关函数结合最大熵数值解析连续方案的多体系统化学反应的量子典范速率常数的计算方法。速率常数表示为实时通量自相关函数的时间积分。实时通量自相关函数通过路径积分蒙特卡洛模拟在短时间内完全量子力学上进行评估。然后,使用最大熵方法从短实时fux自相关数据中提取速率。我们提出了两个数值测试,一个用于光合反应中心在谐波耗散环境中的质子转移。使用通量自相关数据直到不超过#beta#h的时间所获得的结果与在包括隧穿范围在内的各种参数上的电子量子计算都非常吻合。

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