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Study of Si4 and Si<sub>4</sub><sup> - </sup> using threshold photodetachment (ZEKE) spectroscopy

J. Chem. Phys. 99, 3353 (1993); doi:10.1063/1.465145

Issue Date: 1 September 1993

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Caroline C. Arnold and Daniel M. Neumark
Department of Chemistry, University of California, Berkeley, California 94720
Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720
The threshold photodetachment (ZEKE) spectrum of Si<sub>4</sub><sup> - </sup> is presented. Although no transitions to the ground state of Si4 are observed, we obtain detailed information on the anion and several of the low-lying excited states of neutral Si4. The spectrum shows a long progression of well-resolved transitions between the D2h 2B2g rhombus anion and nu2 vibrational levels of the first excited D2h 3B3u neutral. The length and spacing of the progression is consistent with ab initio calculations performed by Rohlfing and Raghavachari [J. Chem. Phys. 96, 2114 (1992)], but some of the sequence bands observed within the progression are not. We also observe transitions to the Si4 1B3u state which is found at a lower excitation energy than predicted. The perturbed vibrational structure in this band is attributed to vibronic coupling to a nearby electronic state which is ``dark'' with respect to ZEKE spectroscopy. The ZEKE spectra are compared to the previously obtained photoelectron spectra of Si<sub>4</sub><sup> - </sup> as well as ab initio calculations on Si<sub>4</sub><sup> - </sup> and Si4. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 19 April 1993; accepted 24 May 1993
Permalink: http://link.aip.org/link/?JCPSA6/99/3353/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.40.+d
    Studies of special atoms and molecules Atomic and molecular clusters
  • 33.80.Gj
    Molecular spectra and interactions of molecules with photons Photon interactions with molecules Diffuse spectra; predissociation, photodissociation
  • 35.80.+s
    Experimentally derived information on atoms and molecules; instrumentation and techniques Atomic and molecular measurement and techniques
  • YEAR: 1993

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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