TY - JOUR
T1 - Relativistic Jahn-Teller effects in the photoelectron spectra of tetrahedral P4, As4, Sb4, and Bi4
AU - Opalka, Daniel
AU - Poluyanov, Leonid V.
AU - Domcke, Wolfgang
N1 - Funding Information:
This work was supported by a research grant of the Deutsche Forschungsgemeinschaft. Computing resources provided by the Leibniz Rechenzentrum of the Bavarian Academy of Sciences are gratefully acknowledged.
PY - 2011/9/14
Y1 - 2011/9/14
N2 - The group-V tetrahedral cluster cations P4+, As 4+, Sb 4+, and Bi 4+ are known to exhibit exceptionally strong Jahn-Teller (JT) effects of electrostatic origin in their 2E ground states and 2T 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 2E and 2T2 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.
AB - The group-V tetrahedral cluster cations P4+, As 4+, Sb 4+, and Bi 4+ are known to exhibit exceptionally strong Jahn-Teller (JT) effects of electrostatic origin in their 2E ground states and 2T 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 2E and 2T2 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.
UR - http://www.scopus.com/inward/record.url?scp=80052955927&partnerID=8YFLogxK
U2 - 10.1063/1.3629779
DO - 10.1063/1.3629779
M3 - Article
AN - SCOPUS:80052955927
SN - 0021-9606
VL - 135
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 10
M1 - 104108
ER -