Theoretical approaches to vibrational quantum dynamics of biomolecules and its control

为了理解包括生物分子在内的相对较大分子的振动运动，通常采用线性（简正模）分析，然而，它缺乏包括振动运动的非线性和非平衡方面，并且不能充分考虑这种运动中的量子效应。时间分辨振动光谱学的最新进展使得人们能够以非常小的时间和空间分辨率检测分子内或分子间的振动能量弛豫（转移）。为了充分理解这种运动，有必要采用更复杂的理论和/或计算方法。在这里，我们提出了使用一个层次的量子态模型称为“一层模型”，这是超越我们以前的努力，使用含时微扰理论，实现了算法作为一个并行代码，并将其应用到最近的实验结果。我们还研究了量子-经典对应下分子的最优控制问题，设计了几种路径采样算法，有效地计算了分子的构象变化。

To understand the vibrational motions of relatively large molecules including biomolecules, a linear (normal mode) analysis is usually employed, however, it lacks to include the nonlinear and nonequilibrium aspects of vibrational motions, and cannot take full account of quantum effects in such a motion. Recent advance in time-resolved vibrational spectroscopy has made it possible to detect vibrational energy relaxation (transfer) within or among molecules with very small time and space resolutions. To fully understand such motions, it is necessary to employ more sophisticated theoretical and/or computational methods. Here we proposed to use a hierarchal quantum state model called “a tier model”, which is beyond our previous effort to use time-dependent perturbation theory, implemented the algorithm as a parallel code, and applied it to recent experimental results. We also studied the optimal control problem of molecules under the light of quantum-classical correspondence, and devised several path sampling algorithms for efficient calculations of conformational change of molecules.