Abstract
Recently, the negative ion photoelectron spectrum of CO 3 - was reported and the second lowest energy band is assigned to the close-lying 3 E′′ and 3 E′ states that undergo Jahn-Teller distortions (Chem. Sci., 2016, 7, 1142). This assignment is based on the Born-Oppenheimer approximation and the assumption of a static Jahn-Teller effect that distorts the CO 3 structure from D 3h to C 2v symmetry. In this work, we employ a 4 states 6 modes vibronic coupling model to investigate the triplet band and uncover the dynamic and non-adiabatic nature of the Jahn-Teller and pseudo-Jahn-Teller interactions in the triplet states. The apparent four peaks progression in the band is studied in depth, and is found to consist of more than four transitions. By comparing the simulated spectra using the full model and the reduced-dimension 2 states 2 modes models, we characterize those transitions. The origin of the complexities of the spectrum is traced to the C-O nonbonding character of the orbitals that lose electron in the photo-detachment process. Methodology-wise, we derive and present the formalisms for arbitrary order expansions of all bimodal trigonal Jahn-Teller and pseudo-Jahn-Teller Hamiltonians in vibrational coordinates.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 8679-8690 |
| Number of pages | 12 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 21 |
| Issue number | 17 |
| DOIs | |
| State | Published - Jan 1 2019 |
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All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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Vibronic interaction in CO 3 - photo-detachment : Jahn-Teller effects beyond structural distortion and general formalisms for vibronic Hamiltonians in trigonal symmetries. / Seidu, Issaka; Goel, Prateek; Wang, Xiao Gang; Chen, Bo; Wang, Xue Bin; Zeng, Tao.
In: Physical Chemistry Chemical Physics, Vol. 21, No. 17, 01.01.2019, p. 8679-8690.Research output: Contribution to journal › Article
TY - JOUR
T1 - Vibronic interaction in CO 3 - photo-detachment
T2 - Jahn-Teller effects beyond structural distortion and general formalisms for vibronic Hamiltonians in trigonal symmetries
AU - Seidu, Issaka
AU - Goel, Prateek
AU - Wang, Xiao Gang
AU - Chen, Bo
AU - Wang, Xue Bin
AU - Zeng, Tao
PY - 2019/1/1
Y1 - 2019/1/1
N2 - Recently, the negative ion photoelectron spectrum of CO 3 - was reported and the second lowest energy band is assigned to the close-lying 3 E′′ and 3 E′ states that undergo Jahn-Teller distortions (Chem. Sci., 2016, 7, 1142). This assignment is based on the Born-Oppenheimer approximation and the assumption of a static Jahn-Teller effect that distorts the CO 3 structure from D 3h to C 2v symmetry. In this work, we employ a 4 states 6 modes vibronic coupling model to investigate the triplet band and uncover the dynamic and non-adiabatic nature of the Jahn-Teller and pseudo-Jahn-Teller interactions in the triplet states. The apparent four peaks progression in the band is studied in depth, and is found to consist of more than four transitions. By comparing the simulated spectra using the full model and the reduced-dimension 2 states 2 modes models, we characterize those transitions. The origin of the complexities of the spectrum is traced to the C-O nonbonding character of the orbitals that lose electron in the photo-detachment process. Methodology-wise, we derive and present the formalisms for arbitrary order expansions of all bimodal trigonal Jahn-Teller and pseudo-Jahn-Teller Hamiltonians in vibrational coordinates.
AB - Recently, the negative ion photoelectron spectrum of CO 3 - was reported and the second lowest energy band is assigned to the close-lying 3 E′′ and 3 E′ states that undergo Jahn-Teller distortions (Chem. Sci., 2016, 7, 1142). This assignment is based on the Born-Oppenheimer approximation and the assumption of a static Jahn-Teller effect that distorts the CO 3 structure from D 3h to C 2v symmetry. In this work, we employ a 4 states 6 modes vibronic coupling model to investigate the triplet band and uncover the dynamic and non-adiabatic nature of the Jahn-Teller and pseudo-Jahn-Teller interactions in the triplet states. The apparent four peaks progression in the band is studied in depth, and is found to consist of more than four transitions. By comparing the simulated spectra using the full model and the reduced-dimension 2 states 2 modes models, we characterize those transitions. The origin of the complexities of the spectrum is traced to the C-O nonbonding character of the orbitals that lose electron in the photo-detachment process. Methodology-wise, we derive and present the formalisms for arbitrary order expansions of all bimodal trigonal Jahn-Teller and pseudo-Jahn-Teller Hamiltonians in vibrational coordinates.
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U2 - 10.1039/c9cp01352k
DO - 10.1039/c9cp01352k
M3 - Article
VL - 21
SP - 8679
EP - 8690
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 17
ER -