Insights in quantum dynamical effects in the infrared spectroscopy of liquid water from a semiclassical study with an ab initio-based flexible and polarizable force field.
Insights in quantum dynamical effects in the infrared spectroscopy of liquid water from a semiclassical study with an ab initio-based flexible and polarizable force field.
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DOI：
10.1063/1.3670960
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发表时间：
2011-12
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通讯作者：
Jian Liu;W. Miller;G. Fanourgakis;S. Xantheas;S. Imoto;S. Saito
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文献类型：
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作者：
Jian Liu;W. Miller;G. Fanourgakis;S. Xantheas;S. Imoto;S. Saito
液态水的动力学性质在自然界的许多过程中起着重要的作用。本文研究了基于局部高斯近似（LGA）的线性化半经典初值表示（LSC-IVR）的液态水红外吸收光谱[J]。刘和W. H. Miller， J. Chem。[j] .地球物理学报，2009,27(5):1104 - 1104。S. Fanourgakis和S. S. Xantheas， J. Chem。物理学报，28(4):555 - 556。虽然LSC-IVR （LGA）给出了孤立的三维位移谐波拉伸模型的精确结果，但它产生了更现实的非谐波拉伸电位的蓝移峰值位置。利用LSC-IVR相关函数的短时信息；然而，它显示了如何获得更准确的拉伸峰位置的结果。由于凝聚态体系存在物理衰减，LSC-IVR （LGA）是一种很好的实用的近似量子方法。目前的结果为未来尝试提高TTM3-F电位或其他基于从头算的模型在再现液态水红外光谱方面的准确性提供了有价值的见解。
The dynamical properties of liquid water play an important role in many processes in nature. In this paper, we focus on the infrared (IR) absorption spectrum of liquid water based on the linearized semiclassical initial value representation (LSC-IVR) with the local Gaussian approximation (LGA) [J. Liu and W. H. Miller, J. Chem. Phys. 131, 074113 (2009)] and an ab initio based, flexible, polarizable Thole-type model (TTM3-F) [G. S. Fanourgakis and S. S. Xantheas, J. Chem. Phys. 128, 074506 (2008)]. Although the LSC-IVR (LGA) gives the exact result for the isolated three-dimensional shifted harmonic stretching model, it yields a blueshifted peak position for the more realistic anharmonic stretching potential. By using the short-time information of the LSC-IVR correlation function; however, it is shown how one can obtain more accurate results for the position of the stretching peak. Due to the physical decay in the condensed phase system, the LSC-IVR (LGA) is a good and practical approximate quantum approach for the IR spectrum of liquid water. The present results offer valuable insight into future attempts to improve the accuracy of the TTM3-F potential or other ab initio-based models in reproducing the IR spectrum of liquid water.