Vibrational solvatochromism and electrochromism: Coarse-grained models and their relationships

被引:75
作者
Cho, Minhaeng [1 ,2 ,3 ]
机构
[1] Korea Univ, Dept Chem, Seoul 136701, South Korea
[2] Korea Univ, Ctr Multidimens Spect, Seoul 136701, South Korea
[3] Korea Basic Sci Inst, Multidimens Spect Lab, Seoul 136713, South Korea
基金
新加坡国家研究基金会;
关键词
electrochromism; electrostatics; infrared spectra; solvation; solvent effects; Stark effect; vibrational states; AMIDE-I MODES; MOLECULAR-STRUCTURE DISTORTIONS; DISTRIBUTED MULTIPOLE ANALYSIS; STARK SPECTROSCOPY; N-METHYLACETAMIDE; ELECTRIC-FIELDS; CIRCULAR-DICHROISM; LIQUID WATER; INFRARED-SPECTROSCOPY; ELECTROSTATIC FIELDS;
D O I
10.1063/1.3079609
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A theoretical description of vibrational solvatochromism and electrochromism is presented by using a coarse-grained model based on a distributed charge and multipole interaction theory. Solvatochromic frequency shift has been described by considering the interaction between distributed charges of a solute and electrostatic potential due to distributed charges of solvent molecules. Another approach was based on the expansion of the solvatochromic frequency shift in terms of solvent electric field and its gradient at distributed sites on solute. The relationship between these two approaches is elucidated and their validities are discussed. It is also shown that the distributed charge and multipole model for solvatochromism developed here can be used to describe vibrational Stark effects on frequency and transition dipole moment. The relationship between the vibrational Stark tuning rate and the parameters obtained from recent vibrational solvatochromism studies is clarified and used to determine the vibrational Stark tuning rates of a few stretching modes, which are then directly compared with experimentally measured values. We anticipate that the present theoretical model can be used to study a variety of vibrational solvatochromic and electrochromic phenomena and to extract critical information on local electrostatic environment around a small IR probe in solution or protein from linear and nonlinear IR spectroscopic studies.
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页数:15
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