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
- Department of Chemistry, University of California, Berkely, CA (USA) Materials and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, CA (USA)
- 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), 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
BOND LENGTHS
EXCITED STATES
FRANCK-CONDON PRINCIPLE
IONIZATION POTENTIAL
JAHN-TELLER EFFECT
L-S COUPLING
MOLECULAR BEAMS
MOLECULAR IONS
PHOTOELECTRON SPECTROSCOPY
VIBRATIONAL STATES
BEAMS
CHARGED PARTICLES
COUPLING
DIMENSIONS
ELECTRON SPECTROSCOPY
ENERGY LEVELS
INTERMEDIATE COUPLING
IONS
LENGTH
SPECTROSCOPY
640302* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory
400201 - Chemical & Physicochemical Properties