Photoelectron spectroscopy and electronic structure of clusters of the group V elements. III. Tetramers: The sup 2 T sub 2 and sup 2 A sub 1 excited 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/10.1063/1.458975· OSTI ID:6314870

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, Berkely, CA (USA) Materials and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, CA (USA)
2. Department of Chemistry, Purdue University, West Lafayette, IN (USA)

Methods employing high resolution HeI (584 A) photoelectron spectroscopy have been applied to the tetrameric clusters of the group V elements, to resolve details of vibronic and spin--orbit structure in the first three electronic states of P{sup +}{sub 4}, As{sup +}{sub 4}, and Sb{sup +}{sub 4}. Measured spacings of distinct vibrational progressions in the {nu}{sub 1} mode for the {sup 2}{ital A}{sub 1} states of P{sup +}{sub 4} and As{sup +}{sub 4}, yield vibrational frequencies of 577 (5) cm{sup {minus}1} for P{sup +}{sub 4} and 350 (6) cm{sup {minus}1} for As{sup +}{sub 4}. Franck--Condon factor calculations suggest bond length changes for the ions in the {sup 2}{ital A}{sub 1} states of 0.054 (3) A for P{sup +}{sub 4} and 0.060 (3) A for As{sup +}{sub 4}. Strong Jahn--Teller distortions in the {nu}{sub 2}({ital e}) vibrational mode dominate the structure of the {sup 2}{ital E} ground states of the tetrameric ions. Both Jahn--Teller and spin--orbit effects appear in the spectra of the {sup 2}{ital T}{sub 2} states of the tetrameric ions, with the spin--orbit effect being dominant in Sb{sup +}{sub 4} and the Jahn--Teller effect dominant in P{sup +}{sub 4}. Vibrational structure is resolved in the P{sup +}{sub 4} spectrum, and the {nu}{sub 3}({ital t}{sub 2}) mode is found to be the one principally active in the Jahn--Teller coupling. A classical metal-droplet model is found to fit well with trends in the IPs of the clusters as a function of size.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6314870
• 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
BOND LENGTHS
CHARGED PARTICLES
COUPLING
DIMENSIONS
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
FRANCK-CONDON PRINCIPLE
INTERMEDIATE COUPLING
IONIZATION POTENTIAL
IONS
JAHN-TELLER EFFECT
L-S COUPLING
LENGTH
MOLECULAR BEAMS
MOLECULAR IONS
PHOSPHORUS IONS
PHOTOELECTRON SPECTROSCOPY
SOLID CLUSTERS
SPECTROSCOPY
VIBRATIONAL STATES