Jet-cooled spectroscopy of the α-methylbenzyl radical: Probing the state-dependent effects of methyl rocking against a radical site

Nathanael M. Kidwell, Neil J. Reilly, Ben Nebgen, Deepali N. Mehta-Hurt, Ross Hoehn, Damian L. Kokkin, Michael C. McCarthy, Lyudmila V. Slipchenko, Timothy S. Zwier

Research output: Contribution to journalArticle

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Abstract

The state-dependent spectroscopy of α-methylbenzyl radical (α-MeBz) has been studied under jet-cooled conditions. Two-color resonant two-photon ionization (2C-R2PI), laser-induced fluorescence, and dispersed fluorescence spectra were obtained for the D0-D1 electronic transition of this prototypical resonance-stabilized radical in which the methyl group is immediately adjacent to the primary radical site. Extensive Franck-Condon activity in hindered rotor levels was observed in the excitation spectrum, reflecting a reorientation of the methyl group upon electronic excitation. Dispersed fluorescence spectra from the set of internal rotor levels are combined with the excitation spectrum to obtain a global fit of the barrier heights and angular change of the methyl group in both D0 and D 1 states. The best-fit methyl rotor potential in the ground electronic state (D0) is a flat-topped 3-fold potential (V 3″ = 151 cm-1, V6″ = 34 cm -1) while the D1 state has a lower barrier (V 3′ = 72 cm-1, V6′ = 15 cm -1) with Δφ = ± π/3, π, consistent with a reorientation of the methyl group upon electronic excitation. The ground state results are compared with calculations carried out at the DFT B3LYP level of theory using the 6-311+G(d,p) basis set, and a variety of excited state calculations are carried out to compare against experiment. The preferred geometry of the methyl rotor in the ground state is anti, which switches to syn in the D1 state and in the cation. The calculations uncover a subtle combination of effects that contribute to the shift in orientation and change in barrier in the excited state relative to ground state. Steric interaction favors the anti conformation, while hyperconjugation is greater in the syn orientation. The presence of a second excited state close by D1 is postulated to influence the methyl rotor properties. A resonant ion-dip infrared (RIDIR) spectrum in the alkyl and aromatic CH stretch regions was also recorded, probing in a complementary way the state-dependent conformation of α-MeBz. Using a scheme in which infrared depletion occurs between excitation and ionization steps of the 2C-R2PI process, analogous infrared spectra in D1 were also obtained, probing the response of the CH stretch fundamentals to electronic excitation. A reduced-dimension Wilson G-matrix model was implemented to simulate and interpret the observed infrared results. Finally, photoionization efficiency scans were carried out to determine the adiabatic ionization threshold of α-MeBz (IP = 6.835 ± 0.002 eV) and provide thresholds for ionization out of specific internal rotor levels, which report on the methyl rotor barrier in the cation state.

Original languageEnglish
Pages (from-to)13465-13480
Number of pages16
JournalJournal of Physical Chemistry A
Volume117
Issue number50
DOIs
Publication statusPublished - 19 Dec 2013
Externally publishedYes

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Spectrum Analysis
Rotors
Fluorescence
Spectroscopy
rotors
Cations
Ionization
spectroscopy
excitation
Excited states
Ground state
Infrared radiation
Photons
ionization
Crystal orientation
electronics
Lasers
Color
Conformations
Ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Jet-cooled spectroscopy of the α-methylbenzyl radical : Probing the state-dependent effects of methyl rocking against a radical site. / Kidwell, Nathanael M.; Reilly, Neil J.; Nebgen, Ben; Mehta-Hurt, Deepali N.; Hoehn, Ross; Kokkin, Damian L.; McCarthy, Michael C.; Slipchenko, Lyudmila V.; Zwier, Timothy S.

In: Journal of Physical Chemistry A, Vol. 117, No. 50, 19.12.2013, p. 13465-13480.

Research output: Contribution to journalArticle

Kidwell, NM, Reilly, NJ, Nebgen, B, Mehta-Hurt, DN, Hoehn, R, Kokkin, DL, McCarthy, MC, Slipchenko, LV & Zwier, TS 2013, 'Jet-cooled spectroscopy of the α-methylbenzyl radical: Probing the state-dependent effects of methyl rocking against a radical site', Journal of Physical Chemistry A, vol. 117, no. 50, pp. 13465-13480. https://doi.org/10.1021/jp406945u
Kidwell, Nathanael M. ; Reilly, Neil J. ; Nebgen, Ben ; Mehta-Hurt, Deepali N. ; Hoehn, Ross ; Kokkin, Damian L. ; McCarthy, Michael C. ; Slipchenko, Lyudmila V. ; Zwier, Timothy S. / Jet-cooled spectroscopy of the α-methylbenzyl radical : Probing the state-dependent effects of methyl rocking against a radical site. In: Journal of Physical Chemistry A. 2013 ; Vol. 117, No. 50. pp. 13465-13480.
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T2 - Probing the state-dependent effects of methyl rocking against a radical site

AU - Kidwell, Nathanael M.

AU - Reilly, Neil J.

AU - Nebgen, Ben

AU - Mehta-Hurt, Deepali N.

AU - Hoehn, Ross

AU - Kokkin, Damian L.

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AU - Zwier, Timothy S.

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N2 - The state-dependent spectroscopy of α-methylbenzyl radical (α-MeBz) has been studied under jet-cooled conditions. Two-color resonant two-photon ionization (2C-R2PI), laser-induced fluorescence, and dispersed fluorescence spectra were obtained for the D0-D1 electronic transition of this prototypical resonance-stabilized radical in which the methyl group is immediately adjacent to the primary radical site. Extensive Franck-Condon activity in hindered rotor levels was observed in the excitation spectrum, reflecting a reorientation of the methyl group upon electronic excitation. Dispersed fluorescence spectra from the set of internal rotor levels are combined with the excitation spectrum to obtain a global fit of the barrier heights and angular change of the methyl group in both D0 and D 1 states. The best-fit methyl rotor potential in the ground electronic state (D0) is a flat-topped 3-fold potential (V 3″ = 151 cm-1, V6″ = 34 cm -1) while the D1 state has a lower barrier (V 3′ = 72 cm-1, V6′ = 15 cm -1) with Δφ = ± π/3, π, consistent with a reorientation of the methyl group upon electronic excitation. The ground state results are compared with calculations carried out at the DFT B3LYP level of theory using the 6-311+G(d,p) basis set, and a variety of excited state calculations are carried out to compare against experiment. The preferred geometry of the methyl rotor in the ground state is anti, which switches to syn in the D1 state and in the cation. The calculations uncover a subtle combination of effects that contribute to the shift in orientation and change in barrier in the excited state relative to ground state. Steric interaction favors the anti conformation, while hyperconjugation is greater in the syn orientation. The presence of a second excited state close by D1 is postulated to influence the methyl rotor properties. A resonant ion-dip infrared (RIDIR) spectrum in the alkyl and aromatic CH stretch regions was also recorded, probing in a complementary way the state-dependent conformation of α-MeBz. Using a scheme in which infrared depletion occurs between excitation and ionization steps of the 2C-R2PI process, analogous infrared spectra in D1 were also obtained, probing the response of the CH stretch fundamentals to electronic excitation. A reduced-dimension Wilson G-matrix model was implemented to simulate and interpret the observed infrared results. Finally, photoionization efficiency scans were carried out to determine the adiabatic ionization threshold of α-MeBz (IP = 6.835 ± 0.002 eV) and provide thresholds for ionization out of specific internal rotor levels, which report on the methyl rotor barrier in the cation state.

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