Photoelectron spectroscopy and electronic structure of clusters of the group V elements. II. Tetramers: Strong Jahn--Teller coupling in the tetrahedral sup 2 E ground states of P sup + sub 4 , As sup + sub 4 , and Sb sup + sub 4
- Department of Chemistry, University of California, Berkeley, CA (USA) Materials and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, CA (USA)
- Department of Chemistry, Purdue University, West Lafayette, IN (USA)
High resolution HeI (584 A) photoelectron spectra have been obtained for the tetrameric clusters of the group V elements: P{sub 4}, As{sub 4}, and Sb{sub 4}. The spectra establish that the ground {sup 2}{ital E} states of tetrahedral P{sup +}{sub 4}, As{sup +}{sub 4}, and Sb{sup +}{sub 4} are unstable with respect to distortion in the {nu}{sub 2}({ital e}) vibrational coordinate. The {ital E}{direct product}e Jahn--Teller problem has been treated in detail, yielding simulated spectra to compare with experimental ones. Vibronic calculations, extended to second order (quadratic coupling) for P{sup +}{sub 4}, account for vibrational structure which is partially resolved in its photoelectron spectrum. A Jahn--Teller stabilization energy of 0.65 eV is derived for P{sup +}{sub 4}, which can be characterized in its ground vibronic state as being highly distorted, and highly fluxional. Linear-only Jahn--Teller coupling calculations performed for As{sup +}{sub 4} and Sb{sup +}{sub 4}, show good qualitative agreement with experimental spectra, yielding stabilization energies of 0.84 and 1.4 eV, respectively.
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6229949
- Journal Information:
- Journal of Chemical Physics; (USA), Vol. 93:9; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANTIMONY IONS
ELECTRONIC STRUCTURE
ARSENIC IONS
PHOSPHORUS IONS
SOLID CLUSTERS
GROUND STATES
JAHN-TELLER EFFECT
MOLECULAR BEAMS
MOLECULAR IONS
PHOTOELECTRON SPECTROSCOPY
BEAMS
CHARGED PARTICLES
ELECTRON SPECTROSCOPY
ENERGY LEVELS
IONS
SPECTROSCOPY
640302* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory
400201 - Chemical & Physicochemical Properties