Vibronic coupling in the ground and excited states of the imidazole radical cation
Vibronic interactions in the ground and two excited states of the imidazole radical cation, X2A″ (π−1), A2A′ (nσ−1), and B2A″ (π−1), and the associated nuclear dynamics were studied theoretically. The results were used to interpret the recent photoelectron measurements [M. Patanen et al., J. Chem. P...
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| Main Authors: | , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
3 November 2022
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| In: |
The journal of chemical physics
Year: 2022, Volume: 157, Issue: 17, Pages: 1-16 |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/5.0118148 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1063/5.0118148 Verlag, lizenzpflichtig, Volltext: https://aip.scitation.org/doi/10.1063/5.0118148 
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| Author Notes: | A.B. Trofimov, A.D. Skitnevskaya, E.K. Grigoricheva, E.V. Gromov, and H. Köppel |
| Summary: | Vibronic interactions in the ground and two excited states of the imidazole radical cation, X2A″ (π−1), A2A′ (nσ−1), and B2A″ (π−1), and the associated nuclear dynamics were studied theoretically. The results were used to interpret the recent photoelectron measurements [M. Patanen et al., J. Chem. Phys. 155, 054304 (2021)]. The present high-level electronic structure calculations employing, in particular, the single, double, and triple excitations and equation-of-motion coupled-cluster method accounting for single and double excitation approaches and complete basis set extrapolation technique for the evaluation of the vertical ionization energies of imidazole indicate that the A 2A′ and B 2A″ states are very close in energy and subject to non-adiabatic effects. Our modeling confirms the existence of pronounced vibronic coupling of the A 2A′ and B 2A″ states. Moreover, despite the large energy gap of nearly 1.3 eV, the ground state X 2A″ is efficiently coupled to the A 2A′ state. The modeling was performed within the framework of the three-state linear vibronic coupling problem employing Hamiltonians expressed in a basis of diabatic electronic states and parameters derived from ab initio calculations. The ionization spectrum was computed using the multi-configuration time-dependent Hartree method. The calculated spectrum is in good agreement with the experimental data, allowing for some interpretation of the observed features to be proposed. |
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| Item Description: | Gesehen am 23.01.2023 |
| Physical Description: | Online Resource |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/5.0118148 |