Relativistic Jahn-Teller effects in the photoelectron spectra of tetrahedral P{sub 4}, As{sub 4}, Sb{sub 4}, and Bi{sub 4}
- Department of Chemistry, Technische Universitaet Muenchen, D-85747 Garching (Germany)
- Institute of Chemical Physics, Academy of Sciences, Chernogolovka, Moscow 142432 (Russian Federation)
The group-V tetrahedral cluster cations P{sub 4}{sup +}, As{sub 4}{sup +}, Sb{sub 4}{sup +}, and Bi{sub 4}{sup +} are known to exhibit exceptionally strong Jahn-Teller (JT) effects of electrostatic origin in their {sup 2}E ground states and {sup 2}T{sub 2} excited states. It has been predicted that there exist, in addition, JT couplings of relativistic origin (arising from the spin-orbit (SO) operator) in {sup 2}E and {sup 2}T{sub 2} states of tetrahedral systems, which should become relevant for the heavier elements. In the present work, the JT and SO couplings in the group-V tetramer cations have been analyzed with ab initio relativistic electronic structure calculations. The vibronic line spectra and the band shapes of the photoelectron spectra were simulated with time-dependent quantum wave-packet methods. The results provide insight into the interplay of electrostatic and relativistic JT couplings and SO splittings in the complex photoelectron spectra of these systems.
- OSTI ID:
- 22038696
- Journal Information:
- Journal of Chemical Physics, Vol. 135, Issue 10; Other Information: (c) 2011 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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