Vibrational solvatochromism. III. Rigorous treatment of the dispersion interaction contribution

A rigorous first principles theory of vibrational solvatochromism including the intermolecular dispersion interaction, which is based on the effective fragment potential method, is developed. The present theory is an extended version of our previous vibrational solvatochromism model that took into a...

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Bibliographic Details
Published in:The Journal of chemical physics 2015-10, Vol.143 (16), p.164111-164111
Main Authors: Błasiak, Bartosz, Cho, Minhaeng
Format: Article
Language:English
Subjects:
Acetamides - chemistry
Biopolymers
Chloroform - chemistry
Computer simulation
Dispersion
Electrochromism
Electrons
Exchanging
First principles
Frequency shift
Hydrogen Bonding
Interaction models
Molecular dynamics
Molecular Dynamics Simulation
Proteins
Solvents
Static Electricity
Water - chemistry
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Summary:A rigorous first principles theory of vibrational solvatochromism including the intermolecular dispersion interaction, which is based on the effective fragment potential method, is developed. The present theory is an extended version of our previous vibrational solvatochromism model that took into account the Coulomb, exchange-repulsion, and induction interactions. We show that the frequency shifts of the amide I mode of N-methylacetamide in H2O and CDCl3, when combined with molecular dynamics simulations, can be quantitatively reproduced by the theory, which indicates that the dispersion interaction contribution to the vibrational frequency shift is not always negligibly small. Nonetheless, the reason that the purely Coulombic interaction model for vibrational solvatochromism works well for describing amide I mode frequency shifts in polar solvents is because the electrostatic contribution is strong and highly sensitive to the relative orientation of surrounding solvent molecules, which is in stark contrast with polarization, dispersion, and exchange-repulsion contributions. It is believed that the theory presented and discussed here will be of great use in quantitatively describing vibrational solvatochromism and electrochromism of infrared probes in not just polar solvent environments but also in biopolymers such as proteins.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4934667