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非平衡定态中的量子动力学速率。

Quantum Kinetic Rates within the Nonequilibrium Steady State.

机构信息

Université Gustave Eiffel, Université Paris Est Creteil, CNRS, UMR 8208, MSME, F-77454 Marne-la-Vallée, France.

Chemical Physics Theory Group, Department of Chemistry, and Center for Quantum Information and Quantum Control, University of Toronto, Toronto, Ontario M5S 3H6, Canada.

出版信息

J Chem Theory Comput. 2023 Feb 28;19(4):1130-1143. doi: 10.1021/acs.jctc.2c00987. Epub 2023 Feb 2.

Abstract

The nonequilibrium steady state (NESS) of a quantum network is central to a host of physical and biological scenarios. Examples include natural processes such as vision and photosynthesis as well as technical devices such as photocells, both activated by incoherent light (e.g., sunlight) and leading to quantum transport. Assessing time scales of the relevant chemical processes in the steady state is thus of utmost interest and is our goal in this paper. Here, a completely general approach to defining components of a quantum network in the NESS and obtaining rates of processes these components is provided. Quantum effects are explicitly included throughout, both in (a) defining network components via projection operators and (b) determining the role of coherences in rate processes. As examples, the methodology is applied to model cases, two versions of the V-level system, and to the spin-boson model, wherein the roles of the environment and of internal system properties in determining the rates are examined. In addition, the role of Markovian vs non-Markovian contributions is quantified, exposing conditions under which NESS rates can be obtained by perturbing the nonequilibrium steady state.

摘要

量子网络的非平衡稳态(NESS)是许多物理和生物场景的核心。例如,自然过程如视觉和光合作用以及技术设备如光电池,都被非相干光(例如阳光)激活,并导致量子输运。因此,评估稳态相关化学过程的时间尺度是非常重要的,这也是我们本文的目标。在这里,我们提供了一种定义 NESS 中量子网络组件的通用方法,并获得了这些组件的过程速率。在整个过程中,量子效应都被明确包括在内,包括 (a) 通过投影算子定义网络组件,以及 (b) 确定相干在速率过程中的作用。作为示例,该方法应用于模型案例、两种 V 级系统版本以及自旋-玻色子模型,其中环境和内部系统特性在确定速率方面的作用被检验。此外,量化了马尔可夫与非马尔可夫贡献的作用,揭示了在何种条件下可以通过微扰非平衡稳态来获得 NESS 速率。

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