振动能弛豫的非马尔可夫理论及其在生物分子系统中的应用
Non-Markovian theory of vibrational energy relaxation and its applications to biomolecular systems
摘要：
能量转移（弛豫）现象在自然界中普遍存在。在宏观层面上，热的唯象理论（傅立叶定律）成功地描述了热传递和能量流动。然而，它的微观起源仍在争论中。这是因为这些现象可以包含多体，多尺度，非平衡，甚至量子力学方面，这对物理，化学和生物学中解决能量转移现象的理论提出了重大挑战。在本文中，我们描述了我们最近的理论尝试，处理振动能量弛豫（VER）的生物分子系统，包括肽，卟啉和蛋白质。首先，我们利用（瞬时）简正模分析构造了一个简化模型，并进一步在振动模式之间加入非谐耦合。使用这样的模型结合含时微扰理论的非谐耦合，我们推导出非马尔可夫VER公式，这是适用于小的时间尺度，如亚皮秒。我们将VER公式应用于各种生物分子系统，讨论VER的时间尺度和机制，并与实验进行比较。最后，我们提到进一步的物理，化学和生物学中的能量转移现象的理论前景。
英文摘要：
Energy transfer (relaxation) phenomena are ubiquitous in nature. At a macroscopic level, the phenomenological theory of heat (Fourier law) successfully describes heat transfer and energy flow. However, its microscopic origin is still under debate. This is because the phenomena can contain many-body, multi-scale, nonequilibrium, and even quantum mechanical aspects, which present significant challenges to theories addressing energy transfer phenomena in physics, chemistry and biology. In this paper, we describe our recent theoretical attempts to treat vibrational energy relaxation (VER) in biomolecular systems, including peptide, porphyrin, and protein. First we construct a reduced model using (instantaneous) normal mode analysis, and further add anharmonic coupling between vibrational modes. Using such a model combined with time-dependent perturbation theory for the anharmonic coupling, we derive non-Markovian VER formulas, which are applicable to small timescales such as sub picoseconds. We apply the VER formulas with full atomistic detail to various biomolecular systems, discuss the VER timescales and mechanisms, and compare with experiment if possible. We finally mention further theoretical prospects of the energy transfer phenomena in physics, chemistry, and biology.
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