Ozer Gungor, Keyes Tom
Department of Chemistry, Boston University, Boston, Massachusetts 02215, United States.
J Phys Chem B. 2015 Jul 23;119(29):9312-8. doi: 10.1021/jp509907v. Epub 2015 Feb 18.
POLIR (POLarizable for IR) (J. Chem. Phys. 2008, 129, 034504) is a polarizable, flexible, and transferable water potential which describes the IR spectrum in the O-H stretch region via the classical dipole correlation function with simple quantum corrections. POLIR also reproduces experimental spectral shifts in solutions of Ca(2+), Mg(2+), and Cu(2+) (J. Am. Chem. Soc. 2011, 133, 9441-9450). Here we present an extended investigation of POLIR water in the solvation shell of the halides F(-), Cl(-), Br(-), and I(-) using various interaction potentials, polarizabilities, and short-range electrostatic damping parameters. Our results indicate that the correlation of the first solvation shell dipoles produces IR spectra that are in agreement with experiment; that is, vibrational spectral shifts may be obtained with classical mechanics and simple corrections. Calculated ion induced dipoles agree with quantum simulations. Further analysis shows that ion-dependent shifts in the spectra may be attributed to the hydrogen bond O···O-H angle distribution within the first solvation shell, decomposed into ion-water and water-water contributions.
POLIR（可极化红外）（《化学物理杂志》2008年，第129卷，034504）是一种可极化、灵活且可转移的水势，它通过具有简单量子修正的经典偶极相关函数来描述O-H伸缩区域的红外光谱。POLIR还能重现Ca(2+)、Mg(2+)和Cu(2+)溶液中的实验光谱位移（《美国化学会志》2011年，第133卷，9441 - 9450）。在此，我们使用各种相互作用势、极化率和短程静电阻尼参数，对卤化物F(-)、Cl(-)、Br(-)和I(-)溶剂化壳层中的POLIR水进行了扩展研究。我们的结果表明，第一溶剂化壳层偶极的相关性产生的红外光谱与实验结果一致；也就是说，振动光谱位移可以通过经典力学和简单修正得到。计算得到的离子诱导偶极与量子模拟结果相符。进一步分析表明，光谱中与离子相关的位移可能归因于第一溶剂化壳层内氢键O···O-H角度分布，可分解为离子 - 水和水 - 水的贡献。
