The electronic spectrum of Si 3 I: Triplet D 3h system

N. J. Reilly, D. L. Kokkin, X. Zhuang, V. Gupta, R. Nagarajan, R. C. Fortenberry, J. P. Maier, Timothy Steimle, J. F. Stanton, M. C. McCarthy

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Abstract

We report the measurement of a jet-cooled electronic spectrum of the silicon trimer. Si 3 was produced in a pulsed discharge of silane in argon, and the excitation spectrum examined in the 18000-20800cm -1 region. A combination of resonant two-color two-photon ionization (R2C2PI) time-of-flight mass spectroscopy, laser-induced fluorescence/dispersed fluorescence, and equation-of-motion coupled-cluster calculations have been used to establish that the observed spectrum is dominated by the 1 3A 1 - ã 3 A 2transition of the D 3h isomer. The spectrum has an origin transition at 18600± 4cm -1 and a short progression in the symmetric stretch with a frequency of ∼445cm -1, in good agreement with a predicted vertical transition energy of 2.34eV for excitation to the 1 3 A 1state, which has a calculated symmetric stretching frequency of 480cm -1. In addition, a ∼505cm -1 ground state vibrational frequency determined from sequence bands and dispersed fluorescence is in agreement with an earlier zero-electron kinetic energy study of the lowest D 3h state and with theory. A weaker, overlapping band system with a ∼360cm -1 progression, observed in the same mass channel (m/z=84) by R2C2PI but under different discharge conditions, is thought to be due to transitions from the (more complicated) singlet C 2v ground state ( 1A 1) state of Si 3. Evidence of emission to this latter state in the triplet dispersed fluorescence spectra suggests extensive mixing in the excited triplet and singlet manifolds. Prospects for further spectroscopic characterization of the singlet system and direct measurement of the energy separation between the lowest singlet and triplet states are discussed.

Original languageEnglish (US)
Article number194307
JournalJournal of Chemical Physics
Volume136
Issue number19
DOIs
StatePublished - May 21 2012

Fingerprint

electronic spectra
Fluorescence
progressions
fluorescence
Ground state
Silanes
Laser spectroscopy
ground state
Argon
Vibrational spectra
Silicon
trimers
Kinetic energy
silanes
Isomers
laser induced fluorescence
atomic energy levels
Stretching
excitation
Equations of motion

ASJC Scopus subject areas

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

Cite this

Reilly, N. J., Kokkin, D. L., Zhuang, X., Gupta, V., Nagarajan, R., Fortenberry, R. C., ... McCarthy, M. C. (2012). The electronic spectrum of Si 3 I: Triplet D 3h system. Journal of Chemical Physics, 136(19), [194307]. https://doi.org/10.1063/1.4704672

The electronic spectrum of Si 3 I : Triplet D 3h system. / Reilly, N. J.; Kokkin, D. L.; Zhuang, X.; Gupta, V.; Nagarajan, R.; Fortenberry, R. C.; Maier, J. P.; Steimle, Timothy; Stanton, J. F.; McCarthy, M. C.

In: Journal of Chemical Physics, Vol. 136, No. 19, 194307, 21.05.2012.

Research output: Contribution to journalArticle

Reilly, NJ, Kokkin, DL, Zhuang, X, Gupta, V, Nagarajan, R, Fortenberry, RC, Maier, JP, Steimle, T, Stanton, JF & McCarthy, MC 2012, 'The electronic spectrum of Si 3 I: Triplet D 3h system', Journal of Chemical Physics, vol. 136, no. 19, 194307. https://doi.org/10.1063/1.4704672
Reilly NJ, Kokkin DL, Zhuang X, Gupta V, Nagarajan R, Fortenberry RC et al. The electronic spectrum of Si 3 I: Triplet D 3h system. Journal of Chemical Physics. 2012 May 21;136(19). 194307. https://doi.org/10.1063/1.4704672
Reilly, N. J. ; Kokkin, D. L. ; Zhuang, X. ; Gupta, V. ; Nagarajan, R. ; Fortenberry, R. C. ; Maier, J. P. ; Steimle, Timothy ; Stanton, J. F. ; McCarthy, M. C. / The electronic spectrum of Si 3 I : Triplet D 3h system. In: Journal of Chemical Physics. 2012 ; Vol. 136, No. 19.
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AU - Gupta, V.

AU - Nagarajan, R.

AU - Fortenberry, R. C.

AU - Maier, J. P.

AU - Steimle, Timothy

AU - Stanton, J. F.

AU - McCarthy, M. C.

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