Experimental investigation of the Jahn-Teller effect in the ground and excited electronic states of the tropyl radical. Part II. Vibrational analysis of the à E3″2 - X̃ E2″2 electronic transition

Ilias Sioutis, Vadim L. Stakhursky, G. Tarczay, Terry A. Miller

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Abstract

Laser-induced fluorescence (LIF) and laser-excited dispersed fluorescence (LEDF) spectra of the cycloheptatrienyl (tropyl) radical C7 H7 have been observed under supersonic jet-cooling conditions. Assignment of the LIF excitation spectrum yields detailed information about the à -state vibronic structure. The LEDF emission was collected by pumping different vibronic bands of the à E3″2 X̃ E2″2 electronic spectrum. Analysis of the LEDF spectra yields valuable information about the vibronic levels of the X̃ E2″2 state. The X̃ - and à -state vibronic structures characterize the Jahn-Teller distortion of the respective potential energy surfaces. A thorough analysis reveals observable Jahn-Teller activity in three of the four e3′ modes for the X̃ E2″2 state and two of the three e1′ modes for the à E3″2 state and provides values for their deperturbed vibrational frequencies as well as linear Jahn-Teller coupling constants. The molecular parameters characterizing the Jahn-Teller interaction in the X̃ and à states of C7 H7 are compared to theoretical results and to those previously obtained for C5 H5 and C6 H6+.

Original languageEnglish
Article number084311
JournalThe Journal of Chemical Physics
Volume128
Issue number8
DOIs
Publication statusPublished - 2008

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Jahn-Teller effect
Electronic states
Fluorescence
fluorescence
laser induced fluorescence
Lasers
electronics
lasers
electronic spectra
pumping
Pumping (laser)
potential energy
Potential energy surfaces
cooling
Vibrational spectra
excitation
Cooling
interactions

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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title = "Experimental investigation of the Jahn-Teller effect in the ground and excited electronic states of the tropyl radical. Part II. Vibrational analysis of the {\~A} E3″2 - X̃ E2″2 electronic transition",
abstract = "Laser-induced fluorescence (LIF) and laser-excited dispersed fluorescence (LEDF) spectra of the cycloheptatrienyl (tropyl) radical C7 H7 have been observed under supersonic jet-cooling conditions. Assignment of the LIF excitation spectrum yields detailed information about the {\~A} -state vibronic structure. The LEDF emission was collected by pumping different vibronic bands of the {\~A} E3″2 X̃ E2″2 electronic spectrum. Analysis of the LEDF spectra yields valuable information about the vibronic levels of the X̃ E2″2 state. The X̃ - and {\~A} -state vibronic structures characterize the Jahn-Teller distortion of the respective potential energy surfaces. A thorough analysis reveals observable Jahn-Teller activity in three of the four e3′ modes for the X̃ E2″2 state and two of the three e1′ modes for the {\~A} E3″2 state and provides values for their deperturbed vibrational frequencies as well as linear Jahn-Teller coupling constants. The molecular parameters characterizing the Jahn-Teller interaction in the X̃ and {\~A} states of C7 H7 are compared to theoretical results and to those previously obtained for C5 H5 and C6 H6+.",
author = "Ilias Sioutis and Stakhursky, {Vadim L.} and G. Tarczay and Miller, {Terry A.}",
year = "2008",
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language = "English",
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journal = "Journal of Chemical Physics",
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TY - JOUR

T1 - Experimental investigation of the Jahn-Teller effect in the ground and excited electronic states of the tropyl radical. Part II. Vibrational analysis of the à E3″2 - X̃ E2″2 electronic transition

AU - Sioutis, Ilias

AU - Stakhursky, Vadim L.

AU - Tarczay, G.

AU - Miller, Terry A.

PY - 2008

Y1 - 2008

N2 - Laser-induced fluorescence (LIF) and laser-excited dispersed fluorescence (LEDF) spectra of the cycloheptatrienyl (tropyl) radical C7 H7 have been observed under supersonic jet-cooling conditions. Assignment of the LIF excitation spectrum yields detailed information about the à -state vibronic structure. The LEDF emission was collected by pumping different vibronic bands of the à E3″2 X̃ E2″2 electronic spectrum. Analysis of the LEDF spectra yields valuable information about the vibronic levels of the X̃ E2″2 state. The X̃ - and à -state vibronic structures characterize the Jahn-Teller distortion of the respective potential energy surfaces. A thorough analysis reveals observable Jahn-Teller activity in three of the four e3′ modes for the X̃ E2″2 state and two of the three e1′ modes for the à E3″2 state and provides values for their deperturbed vibrational frequencies as well as linear Jahn-Teller coupling constants. The molecular parameters characterizing the Jahn-Teller interaction in the X̃ and à states of C7 H7 are compared to theoretical results and to those previously obtained for C5 H5 and C6 H6+.

AB - Laser-induced fluorescence (LIF) and laser-excited dispersed fluorescence (LEDF) spectra of the cycloheptatrienyl (tropyl) radical C7 H7 have been observed under supersonic jet-cooling conditions. Assignment of the LIF excitation spectrum yields detailed information about the à -state vibronic structure. The LEDF emission was collected by pumping different vibronic bands of the à E3″2 X̃ E2″2 electronic spectrum. Analysis of the LEDF spectra yields valuable information about the vibronic levels of the X̃ E2″2 state. The X̃ - and à -state vibronic structures characterize the Jahn-Teller distortion of the respective potential energy surfaces. A thorough analysis reveals observable Jahn-Teller activity in three of the four e3′ modes for the X̃ E2″2 state and two of the three e1′ modes for the à E3″2 state and provides values for their deperturbed vibrational frequencies as well as linear Jahn-Teller coupling constants. The molecular parameters characterizing the Jahn-Teller interaction in the X̃ and à states of C7 H7 are compared to theoretical results and to those previously obtained for C5 H5 and C6 H6+.

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