液态硝基苯中的取向关联与局部场

Orientation correlation and local field in liquid nitrobenzene.

作者信息

Shelton David P

机构信息

Department of Physics and Astronomy, University of Nevada, Las Vegas, Nevada 89154-4002, USA.

出版信息

J Chem Phys. 2016 Jun 21;144(23):234506. doi: 10.1063/1.4953794.

DOI:10.1063/1.4953794

PMID:27334178

Abstract

Hyper-Rayleigh scattering (HRS) is sensitive to long-range molecular orientation correlation in isotropic liquids composed of dipolar molecules. Measurements of the polarization, angle, and spectral dependence for HRS from liquid nitrobenzene (NB) are analyzed to determine the NB molecular orientation correlations at long range. The longitudinal and transverse orientation correlation functions for r > 3 nm are BL(r) = (a/r)(3) and BT(r) = - BL(r)/2, where a = 0.20 ± 0.01 nm. Measurements of HRS induced by dissolved ions are also analyzed and combined with molecular dynamics simulation and dielectric response results, to determine the molecular dipole moment μ = 3.90 ± 0.04 D, Kirkwood orientation correlation factor gK = 0.68 ± 0.02, and local field factor f(0) = 0.85 ± 0.04 × Onsager local field factor in liquid nitrobenzene.

摘要

超瑞利散射（HRS）对由偶极分子组成的各向同性液体中的长程分子取向相关性敏感。对液态硝基苯（NB）的HRS的偏振、角度和光谱依赖性测量进行了分析，以确定长程下的NB分子取向相关性。对于r > 3 nm，纵向和横向取向相关函数分别为BL(r) = (a/r)(3) 和BT(r) = - BL(r)/2，其中a = 0.20 ± 0.01 nm。还对溶解离子诱导的HRS测量进行了分析，并与分子动力学模拟和介电响应结果相结合，以确定液态硝基苯中的分子偶极矩μ = 3.90 ± 0.04 D、柯克伍德取向相关因子gK = 0.68 ± 0.02以及局部场因子f(0) = 0.85 ± 0.04 × 昂萨格局部场因子。