Vibrational solvatochromism and electrochromism. II. Multipole analysis

Hochan Lee, Jun Ho Choi, Minhaeng Cho

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

Small infrared probe molecules have been widely used to study local electrostatic environment in solutions and proteins. Using a variety of time- and frequency-resolved vibrational spectroscopic methods, one can accurately measure the solvation-induced vibrational frequency shifts and the timescales and amplitudes of frequency fluctuations of such IR probes. Since the corresponding frequency shifts are directly related to the local electric field and its spatial derivatives of the surrounding solvent molecules or amino acids in proteins, one can extract information on local electric field around an IR probe directly from the vibrational spectroscopic results. Here, we show that, carrying out a multipole analysis of the solvatochromic frequency shift, the solvatochromic dipole contribution to the frequency shift is not always the dominant factor. In the cases of the nitrile-, thiocyanato-, and azido-derivatized molecules, the solvatochromic quadrupole contributions to the corresponding stretch mode frequency shifts are particularly large and often comparable to the solvatochromic dipole contributions. Noting that the higher multipole moment-solvent electric field interactions are short range effects in comparison to the dipole interaction, the H-bonding interaction-induced vibrational frequency shift can be caused by such short-range multipole-field interaction effects. We anticipate that the present multipole analysis method specifically developed to describe the solvatochromic vibrational frequency shifts will be useful to understand the intermolecular interaction-induced vibrational property changes and to find out a relationship between vibrational solvatochromism and electrochromism of IR probes in condensed phases.

Original languageEnglish
Article number114307
JournalJournal of Chemical Physics
Volume137
Issue number11
DOIs
Publication statusPublished - 2012 Sep 21

Fingerprint

Electrochromism
electrochromism
Vibrational spectra
multipoles
frequency shift
Electric fields
Molecules
probes
Nitriles
dipoles
Solvation
interactions
electric fields
Electrostatics
Proteins
proteins
molecules
Infrared radiation
Derivatives
Amino Acids

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Vibrational solvatochromism and electrochromism. II. Multipole analysis. / Lee, Hochan; Choi, Jun Ho; Cho, Minhaeng.

In: Journal of Chemical Physics, Vol. 137, No. 11, 114307, 21.09.2012.

Research output: Contribution to journalArticle

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