Accidental vibrational degeneracy in vibrational excited states observed with ultrafast two-dimensional IR vibrational echo spectroscopy

Junrong Zheng, Kyungwon Kwak, Tobias Steinel, John Asbury, Xin Chen, Jia Xie, M. D. Fayer

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The coupling between the OD stretch v=2 level and benzene-ring modes in 2-methoxyphenol-OD (hydroxyl H replaced by D) is observed with ultrafast two-dimensional (2D) IR vibrational echo spectroscopy. Because of this coupling, the 1-2 transition peak in the 2D spectrum is split into a doublet with peaks of approximately equal amplitudes. Several molecules and solvents were used to study this phenomenon. Near-IR (NIR) spectroscopy measurements and density-functional theory calculations (B3LYP6-31+G (d,p) level) were also applied. Experimental results and calculations show that the OD stretch 1-2 transition is coupled to a combination band related to the benzene-ring motions. A simple quantum-mechanical model indicates that the combination band has a frequency of 5172 and 5176.5 cm-1 in C Cl4 and hexane, respectively. The transition between this combination band and the ground state is too weak to detect by NIR. The transition between this band and the OD stretch first excited state is also so weak that most of the intensity of the doublet comes from the oscillator strength produced by coupling to the OD stretch. The model gives the coupling strengths as 6.5 and 7 cm-1 in C Cl4 and hexane, respectively.

Original languageEnglish (US)
Article number164301
JournalJournal of Chemical Physics
Volume123
Issue number16
DOIs
StatePublished - Nov 7 2005

Fingerprint

Hexanes
Benzene
Excited states
echoes
Spectroscopy
Guaiacol
Electron transitions
Hydroxyl Radical
Ground state
spectroscopy
excitation
Density functional theory
Infrared spectroscopy
benzene
Molecules
rings
oscillator strengths
density functional theory
ground state
molecules

All Science Journal Classification (ASJC) codes

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

Cite this

Zheng, Junrong ; Kwak, Kyungwon ; Steinel, Tobias ; Asbury, John ; Chen, Xin ; Xie, Jia ; Fayer, M. D. / Accidental vibrational degeneracy in vibrational excited states observed with ultrafast two-dimensional IR vibrational echo spectroscopy. In: Journal of Chemical Physics. 2005 ; Vol. 123, No. 16.
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abstract = "The coupling between the OD stretch v=2 level and benzene-ring modes in 2-methoxyphenol-OD (hydroxyl H replaced by D) is observed with ultrafast two-dimensional (2D) IR vibrational echo spectroscopy. Because of this coupling, the 1-2 transition peak in the 2D spectrum is split into a doublet with peaks of approximately equal amplitudes. Several molecules and solvents were used to study this phenomenon. Near-IR (NIR) spectroscopy measurements and density-functional theory calculations (B3LYP6-31+G (d,p) level) were also applied. Experimental results and calculations show that the OD stretch 1-2 transition is coupled to a combination band related to the benzene-ring motions. A simple quantum-mechanical model indicates that the combination band has a frequency of 5172 and 5176.5 cm-1 in C Cl4 and hexane, respectively. The transition between this combination band and the ground state is too weak to detect by NIR. The transition between this band and the OD stretch first excited state is also so weak that most of the intensity of the doublet comes from the oscillator strength produced by coupling to the OD stretch. The model gives the coupling strengths as 6.5 and 7 cm-1 in C Cl4 and hexane, respectively.",
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Accidental vibrational degeneracy in vibrational excited states observed with ultrafast two-dimensional IR vibrational echo spectroscopy. / Zheng, Junrong; Kwak, Kyungwon; Steinel, Tobias; Asbury, John; Chen, Xin; Xie, Jia; Fayer, M. D.

In: Journal of Chemical Physics, Vol. 123, No. 16, 164301, 07.11.2005.

Research output: Contribution to journalArticle

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