Electronic States of the Benzene Dimer: A Simple Case of Complexity
| Autor: | Anna I. Krylov, Kadir Diri |
|---|---|
| Rok vydání: | 2011 |
| Předmět: |
Valence (chemistry)
Absorption spectroscopy Oscillator strength Dimer Electronic structure Photochemistry Excimer Molecular physics chemistry.chemical_compound symbols.namesake chemistry Excited state Physics::Atomic and Molecular Clusters Rydberg formula symbols Physics::Atomic Physics Physical and Theoretical Chemistry |
| Zdroj: | The Journal of Physical Chemistry A. 116:653-662 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp209190e |
| Popis: | Electronic structure calculations of the excited states of the benzene dimer using equation-of-motion coupled-cluster method are reported. The calculations reveal large density of electronic states, including multiple valence, Rydberg, and mixed Rydberg-valence states. The calculations of the oscillator strengths for the transitions between the excimer state (i.e., the lowest excited state of the dimer, 1(1)B(1g)) and other excited states allowed us to identify the target state responsible for the excimer absorption as the E(1u) state of a mixed Rydberg-valence character at 3.04 eV above the excimer (1(1)B(1g)). Although at D(6h) the 1(1)B(1g) → E(1u) transition is symmetry-forbidden, small geometric displacements (to D(2h)) that have a negligible effect on the excitation energy split this degenerate state into the dark (4B(3u)) and bright (4B(2u)) components (oscillator strength of 0.3 au). The excitation energy for this transition depends strongly on the dimer structure, which explains the broad character of the experimentally observed excimer absorption spectrum. |
| Databáze: | OpenAIRE |
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