Quantum State-to-State Rates for Multistate Processes from Coherences
Quantum State-to-State Rates for Multistate Processes from Coherences
复制标题
来自相干性的多状态过程的量子状态到状态速率
DOI：
10.1021/acs.jpclett.2c02286
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Makri, Nancy
中科院分区：
文献类型：
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作者：
Dani, Reshmi;Makri, Nancy
对于通过系统基中的局部项耦合到一般环境的多态系统，我们证明了种群的时间导数是以相干性的虚分量给出的，即，简化密度矩阵的非对角元素。当该过程表现出速率动力学，我们表明，所有的状态到状态的速率可以从这些虚部的早期“高原”值。然后从短时模拟结果和动力学方程的解与计算的速率矩阵的状态人口的演变。这些表达式概括了反应通量方法和它的非平衡态版本的多状态过程，并表明，即使在完全不相干的限制率动力学，人口的时间演化是由凝聚力。此外，我们表明，凭借详细的平衡，短时间内的价值观的虚部coherently完全确定的平衡人口。
For a multistate system coupled to a general environment through terms local in the system basis, we show that the time derivatives of populations are given in terms of imaginary components of coherences, i.e., off-diagonal elements of the reduced density matrix. When the process exhibits rate dynamics, we show that all state-to-state rates can be obtained from the early “plateau” values of these imaginary components. The evolution of the state populations is then obtained from the short-time simulation results and the solution of the kinetic equations with the computed rate matrix. These expressions generalize the reactive flux method and its nonequilibrium version to multistate processes and show that even in the completely incoherent limit of rate kinetics, the time evolution of populations is governed by coherences. Further, we show that by virtue of detailed balance, the short-time values of the imaginary components of coherences fully determine the equilibrium populations.