First Principles Simulations of the Infrared Spectrum of Liquid Water Using Hybrid Density Functionals

详细信息    查看全文

• 作者：Cui Zhang ; Davide Donadio ; Franc抬ois Gygi ; Giulia Galli
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2011
• 出版时间：May 10, 2011
• 年：2011
• 卷：7
• 期：5
• 页码：1443-1449
• 全文大小：807K
• 年卷期：v.7,no.5(May 10, 2011)
• ISSN：1549-9626

文摘

We show that first principles hybrid functional (PBE0) simulations of the infrared spectrum of liquid water yields a much better agreement with experimental results than a semilocal functional description; in particular, the quantitative accord with measured stretching and bending bands is very good. Such an improved description stems from two effects: a more accurate account, at the PBE0 level of theory, of the vibrational properties of the monomer and dimer and an underlying structural model for the liquid with a smaller number of hydrogen bonds and oxygen coordination than those obtained with semilocal functionals. The average electronic gap of the liquid is increased by 60% with respect to the PBE value, when computed at the PBE0 level of theory, and is in fair agreement with experimental results.