Vibrational solvatochromism. II. A first-principle theory of solvation-induced vibrational frequency shift based on effective fragment potential method
- Authors
- Blasiak, Bartosz; Cho, Minhaeng
- Issue Date
- 28-4월-2014
- Publisher
- AMER INST PHYSICS
- Citation
- JOURNAL OF CHEMICAL PHYSICS, v.140, no.16
- Indexed
- SCIE
SCOPUS
- Journal Title
- JOURNAL OF CHEMICAL PHYSICS
- Volume
- 140
- Number
- 16
- URI
- https://scholar.korea.ac.kr/handle/2021.sw.korea/98732
- DOI
- 10.1063/1.4872040
- ISSN
- 0021-9606
- Abstract
- Vibrational solvatochromism is a solvation-induced effect on fundamental vibrational frequencies of molecules in solutions. Here we present a detailed first-principle coarse-grained theory of vibrational solvatochromism, which is an extension of our previous work [B. Blasiak, H. Lee, and M. Cho, J. Chem. Phys. 139(4), 044111 (2013)] by taking into account electrostatic, exchange-repulsion, polarization, and charge-transfer interactions. By applying our theory to the model N-methylacetamide-water clusters, solute-solvent interaction-induced effects on amide I vibrational frequency are fully elucidated at Hartree-Fock level. Although the electrostatic interaction between distributed multipole moments of solute and solvent molecules plays the dominant role, the contributions from exchange repulsion and induced dipole-electric field interactions are found to be of comparable importance in short distance range, whereas the charge-transfer effect is negligible. The overall frequency shifts calculated by taking into account the contributions of electrostatics, exchange-repulsion, and polarization terms are in quantitative agreement with ab initio results obtained at the Hartree-Fock level of theory. (C) 2014 AIP Publishing LLC.
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