A Polarizable Water Model for Intramolecular and Intermolecular Vibrational Spectroscopies
A Polarizable Water Model for Intramolecular and Intermolecular Vibrational Spectroscopies
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DOI：
10.1021/jp111308f
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发表时间：
2011-05-12
影响因子：
3.3
通讯作者：
Tanimura, Yoshitaka
中科院分区：
文献类型：
--
作者：
Hasegawa, Taisuke;Tanimura, Yoshitaka
我们已经开发了一个极化水模型的经典分子动力学模拟的振动光谱，它涵盖了从低频分子间的模式，高频分子内的振动模式。该模型利用从头算推导的几何相关的多极矩表面来描绘的瞬时电荷密度的水分子。永久多极子包括多极子到四极子，而感应多极子包括偶极子。分子的极化由分布极化率模型描述。在室温下，本模型是能够重现实验红外和拉曼光谱的分子内振动模式，除了蓝峰位移由于限制的经典模拟的基础上的量子力学势。计算的低频分子间模式的红外光谱与实验信号相当吻合。
We have developed a polarizable water model for classical molecular dynamics simulations of vibrational spectroscopies, which covers from low-frequency intermolecular modes to high-frequency intramolecular vibrational modes. The model utilizes the ab initio derived geometry-dependent multipole moment surfaces to depict the instantaneous charge density of a water molecule. Multipoles up to quadrupole are included for the permanent multipoles, while those up to dipole are included for the induced multipoles. The polarization of molecules is described by a distributed polarizability model. At room temperature, the present model is able to reproduce experimental infrared and Raman spectra of intramolecular vibrational modes, except for the blue peak shift due to a limitation of the classical simulation based on a quantum mechanical potential. The calculated infrared spectrum for low-frequency intermolecular modes agreed reasonably well with the experimental signals.