Laser-induced fluorescence spectroscopy of jet-cooled 2-methylanthracene S1 (π,π*). Evidence for methyl conformation change upon electronic excitation

H. Lin, J. A. Hunter, J. Pfab

Research output: Contribution to journalArticle

Abstract

The laser-induced fluorescence excitation spectrum of jet-cooled 2-methylanthracene (2-MA) near the S1-So origin reveals a prominent torsional progression due to the internal rotation of the methyl group or its torsional vibration against the aromatic ring frame. From the torsional level spacings a low, threefold hindered internal rotation barrier of 70 cm-1 has been determined for S1(p,p*). A Frank-Condon intensity analysis of the progression in the excited state torsion suggests that the most stable rotamer of 2-MA changes from an eclipsed-staggered (e-s) conformation in the electronic ground state to a (s-e) conformation in the first singlet excited state. This 60° change in the dihedral conformation can be rationalized by the change of the p-bond order of the adjacent ring bonds upon electronic excitation, such that one of the CH methyl bonds prefer to eclipse the adjacent CC bond with the stronger p-bond character. © 1993.

Original languageEnglish
Pages (from-to)38-44
Number of pages7
JournalChemical Physics Letters
Volume210
Issue number1-3
Publication statusPublished - 23 Jul 1993

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Fluorescence spectroscopy
Conformations
Excited states
Lasers
Torsional stress
Ground state
Fluorescence
2-methylanthracene

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title = "Laser-induced fluorescence spectroscopy of jet-cooled 2-methylanthracene S1 (π,π*). Evidence for methyl conformation change upon electronic excitation",
abstract = "The laser-induced fluorescence excitation spectrum of jet-cooled 2-methylanthracene (2-MA) near the S1-So origin reveals a prominent torsional progression due to the internal rotation of the methyl group or its torsional vibration against the aromatic ring frame. From the torsional level spacings a low, threefold hindered internal rotation barrier of 70 cm-1 has been determined for S1(p,p*). A Frank-Condon intensity analysis of the progression in the excited state torsion suggests that the most stable rotamer of 2-MA changes from an eclipsed-staggered (e-s) conformation in the electronic ground state to a (s-e) conformation in the first singlet excited state. This 60° change in the dihedral conformation can be rationalized by the change of the p-bond order of the adjacent ring bonds upon electronic excitation, such that one of the CH methyl bonds prefer to eclipse the adjacent CC bond with the stronger p-bond character. {\circledC} 1993.",
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Laser-induced fluorescence spectroscopy of jet-cooled 2-methylanthracene S1 (π,π*). Evidence for methyl conformation change upon electronic excitation. / Lin, H.; Hunter, J. A.; Pfab, J.

In: Chemical Physics Letters, Vol. 210, No. 1-3, 23.07.1993, p. 38-44.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Laser-induced fluorescence spectroscopy of jet-cooled 2-methylanthracene S1 (π,π*). Evidence for methyl conformation change upon electronic excitation

AU - Lin, H.

AU - Hunter, J. A.

AU - Pfab, J.

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N2 - The laser-induced fluorescence excitation spectrum of jet-cooled 2-methylanthracene (2-MA) near the S1-So origin reveals a prominent torsional progression due to the internal rotation of the methyl group or its torsional vibration against the aromatic ring frame. From the torsional level spacings a low, threefold hindered internal rotation barrier of 70 cm-1 has been determined for S1(p,p*). A Frank-Condon intensity analysis of the progression in the excited state torsion suggests that the most stable rotamer of 2-MA changes from an eclipsed-staggered (e-s) conformation in the electronic ground state to a (s-e) conformation in the first singlet excited state. This 60° change in the dihedral conformation can be rationalized by the change of the p-bond order of the adjacent ring bonds upon electronic excitation, such that one of the CH methyl bonds prefer to eclipse the adjacent CC bond with the stronger p-bond character. © 1993.

AB - The laser-induced fluorescence excitation spectrum of jet-cooled 2-methylanthracene (2-MA) near the S1-So origin reveals a prominent torsional progression due to the internal rotation of the methyl group or its torsional vibration against the aromatic ring frame. From the torsional level spacings a low, threefold hindered internal rotation barrier of 70 cm-1 has been determined for S1(p,p*). A Frank-Condon intensity analysis of the progression in the excited state torsion suggests that the most stable rotamer of 2-MA changes from an eclipsed-staggered (e-s) conformation in the electronic ground state to a (s-e) conformation in the first singlet excited state. This 60° change in the dihedral conformation can be rationalized by the change of the p-bond order of the adjacent ring bonds upon electronic excitation, such that one of the CH methyl bonds prefer to eclipse the adjacent CC bond with the stronger p-bond character. © 1993.

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