First-principles study of the infrared spectrum in liquid water from a systematically improved description of H-bond network

Jianhang Xu, Mohan Chen, Cui Zhang, and Xifan Wu
Phys. Rev. B 99, 205123 – Published 14 May 2019

Abstract

An accurate ab initio theory of the H-bond structure of liquid water requires a high-level exchange correlation approximation from density functional theory. Based on the liquid structures modeled by ab initio molecular dynamics by using maximally localized Wannier functions as a basis, we study the infrared spectrum of water within the canonical ensemble. In particular, we employ both the Perdew-Burke-Ernzerhof (PBE) functional within the generalized gradient approximation (GGA) and the state-of-the-art meta-GGA level approximation provided by the strongly constrained and appropriately normed (SCAN) functional. We demonstrate that the SCAN functional improves not only the water structure but also the theoretical infrared spectrum of water. Our analyses show that the improvement in the stretching and bending bands can be mainly attributed to better descriptions of directional H bonding and the covalency at the inter- and intramolecular levels, respectively. On the other hand, better agreements in libration and hindered translation bands are due to the improved dynamics of the H-bond network enabled by a less structured liquid in the experimental direction. The spectrum predicted by SCAN shows much better agreement with experimental data than the conventionally widely adopted PBE functional at the GGA level.

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  • Received 19 February 2019
  • Revised 18 April 2019

DOI:https://doi.org/10.1103/PhysRevB.99.205123

©2019 American Physical Society

Physics Subject Headings (PhySH)

Atomic, Molecular & Optical

Authors & Affiliations

Jianhang Xu1, Mohan Chen2, Cui Zhang3, and Xifan Wu1,4

  • 1Department of Physics, Temple University, Philadelphia, Pennsylvania 19122, USA
  • 2CAPT, HEDPS, College of Engineering, Peking University, Beijing 100871, China
  • 3Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
  • 4Institute for Computational Molecular Science, Temple University, Philadelphia, Pennsylvania 19122, USA

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Issue

Vol. 99, Iss. 20 — 15 May 2019

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