Ultrafast intermoleailar vibrational excitation transfer from solute to solvent

Observation of intermediate states

Hyewon Son, Kwang Hee Park, Kyungwon Kwak, Sungnam Park, Minhaeng Cho

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Ultrafast two-dimensional infrared (2DIR) and IR pump-probe (PP) spectroscopy was used to study the intermolecular vibrational energy transfer process from the excited state of asymmetric stretching vibration of HN3 to the overtone band of C-O stretching vibration of solvent methanol. A series of time- resolved 2DIR spectra indicate an intermolecular vibrational excitation transfer between the two modes, since the corresponding cross peaks appear at longer waiting times (>20 ps). However, detailed analyses of temperature-dependent FTIR, dispersed IR PP, and 2DIR spectra showed that the vibrational relaxation of the azido stretch mode and its energy transfer to solvent methanol C-O stretch overtone mode involve not only heat dissipation directly to the solvent bath modes but also production of transient intermediate states. The present experimental work demonstrates that ultrafast nonlinear IR spectroscopy is quite useful to shed light into the complicated vibrational relaxation dynamics of H-bonded solute-solvent systems.

Original languageEnglish
Pages (from-to)37-46
Number of pages10
JournalChemical Physics
Volume422
DOIs
Publication statusPublished - 2013 Apr 23

Fingerprint

solutes
molecular relaxation
Energy transfer
Stretching
excitation
Methanol
methyl alcohol
energy transfer
Pumps
pumps
harmonics
vibration
probes
Heat losses
Excited states
spectroscopy
Infrared spectroscopy
baths
Spectroscopy
Infrared radiation

Keywords

  • IR spectroscopy
  • Two-dimensional
  • Vibrational energy transfer
  • Vibrational relaxation

ASJC Scopus subject areas

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

Cite this

Ultrafast intermoleailar vibrational excitation transfer from solute to solvent : Observation of intermediate states. / Son, Hyewon; Park, Kwang Hee; Kwak, Kyungwon; Park, Sungnam; Cho, Minhaeng.

In: Chemical Physics, Vol. 422, 23.04.2013, p. 37-46.

Research output: Contribution to journalArticle

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AU - Cho, Minhaeng

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AB - Ultrafast two-dimensional infrared (2DIR) and IR pump-probe (PP) spectroscopy was used to study the intermolecular vibrational energy transfer process from the excited state of asymmetric stretching vibration of HN3 to the overtone band of C-O stretching vibration of solvent methanol. A series of time- resolved 2DIR spectra indicate an intermolecular vibrational excitation transfer between the two modes, since the corresponding cross peaks appear at longer waiting times (>20 ps). However, detailed analyses of temperature-dependent FTIR, dispersed IR PP, and 2DIR spectra showed that the vibrational relaxation of the azido stretch mode and its energy transfer to solvent methanol C-O stretch overtone mode involve not only heat dissipation directly to the solvent bath modes but also production of transient intermediate states. The present experimental work demonstrates that ultrafast nonlinear IR spectroscopy is quite useful to shed light into the complicated vibrational relaxation dynamics of H-bonded solute-solvent systems.

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