The state-to-state rate of vibrational energy relaxation of the OH-stretch fundamental is investigated via perturbative methods. The system is separated into an 11 degree of freedom methanol molecule and the surrounding bath. Notably, the large amplitude torsional motion is considered a bath degree of freedom, and the 11 small amplitude normal modes are expanded in a Fourier series of the torsional angle. The methanol-bath coupling is computed through the use of a molecular dynamics simulation, and the results are computed using Landau-Teller and time dependent perturbation theory. Results are compared to the ultrafast pump-probe experiments of L. K. Iwaki and D. D. Dlott [J. Phys. Chem. A 2000, 104, 9101].
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机译：通过微扰方法研究了OH拉伸基体的振动能弛豫状态速率。该系统分为11个自由度的甲醇分子和周围的浴。值得注意的是，大振幅扭转运动被认为是浴的自由度，并且11种小振幅法向模式以扭转角的傅里叶级数展开。通过使用分子动力学模拟计算甲醇-浴耦合，并使用Landau-Teller和时间相关的扰动理论计算结果。将结果与L. K. Iwaki和D. D. Dlott的超快泵浦探针实验进行了比较[J.物理化学A 2000，104，9101]。
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