Stochastic Liouville equations for hydrogen-bonding fluctuations and their signatures in two-dimensional vibrational spectroscopy of water
Stochastic Liouville equations for hydrogen-bonding fluctuations and their signatures in two-dimensional vibrational spectroscopy of water
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DOI：
10.1063/1.2008251
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发表时间：
2005-09-15
影响因子：
4.4
通讯作者：
Mukamel, S
中科院分区：
文献类型：
--
作者：
Jansen, TL;Hayashi, T;Mukamel, S
氢键的形成和断裂动力学对D2O中HOD的OH伸展的线性和相干三阶红外光谱的影响可用马尔科夫涨落描述，不一定是高斯涨落，并用随机Liouville方程模拟。慢(0.5ps)起伏由集体静电坐标表示，而快速(<；100ps)频率起伏则使用第二集体静电坐标或氢键构型的四态跳跃(FSJ)模型来描述。这两个模型的参数都是通过使用TIP4P力场和静电从头算图计算的1 ns分子动力学轨迹获得的。FSJ预测的光子回波光谱的不对称性(蓝边比红边更宽)与最近的实验更吻合。(C)2005年美国物理研究所。
The effects of hydrogen-bond forming and breaking kinetics on the linear and coherent third-order infrared spectra of the OH stretch of HOD in D2O are described by Markovian, not necessarily Gaussian, fluctuations and simulated using the stochastic Liouville equations. Slow (0.5 ps) fluctuations are represented by a collective electrostatic coordinate, whereas fast (< 100 fs) frequency fluctuations are described using either a second collective electrostatic coordinate or a four-state jump (FSJ) model for hydrogen-bonding configurations. Parameters for both models were obtained using a 1-ns molecular-dynamics trajectory calculated using the TIP4P force field combined with an electrostatic ab initio map. The asymmetry of the photon-echo spectra (larger linewidth on the blue side than on the red side) predicted by the FSJ is in better agreement with recent experiments. (c) 2005 American Institute of Physics.