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

Journal Article · Thu Nov 01 00:00:00 EST 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.459698· OSTI ID:6229949

Wang, L; Niu, B; Lee, Y T; Shirley, D A ^[1]; Ghelichkhani, E; Grant, E R ^[2]

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1. Department of Chemistry, University of California, Berkeley, CA (USA) Materials and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, CA (USA)
2. 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), Journal Name: Journal of Chemical Physics; (USA) Vol. 93:9; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ANTIMONY IONS
ARSENIC IONS
BEAMS
CHARGED PARTICLES
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY LEVELS
GROUND STATES
IONS
JAHN-TELLER EFFECT
MOLECULAR BEAMS
MOLECULAR IONS
PHOSPHORUS IONS
PHOTOELECTRON SPECTROSCOPY
SOLID CLUSTERS
SPECTROSCOPY