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
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) [Liu and Miller, J. Chem. Phys. 131, 074113 (2009)] and an ab initio based, flexible, polarizable Thole-type model (TTM3-F) [Fanourgakis and Xantheas, J. Chem. Phys. 128, 074506 (2008)]. Although the LSC-IVR (LGA) gives the exact result for the isolated 3-dimensional shifted harmonic stretching model, it yields a blue-shifted peak position for the more realistic anharmonic stretching potential. By using the short time information of the LSCIVR 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 in reproducing the IR spectrum of liquid water.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1044510
- Report Number(s):
- PNNL-SA-82605; JCPSA6; KC0301020; TRN: US201214%%469
- Journal Information:
- Journal of Chemical Physics, Vol. 135, Issue 24; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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