Schweke, D. and Haas, Y. and Dick, Bernhard (2005) Photophysics of phenylpyrrole derivatives and their acetonitrile clusters in the gas phase and in argon matrixes: Simulations of structure and reactivity. JOURNAL OF PHYSICAL CHEMISTRY A, 109 (17). pp. 3830-3842. ISSN 1089-5639,
Full text not available from this repository.Abstract
Recent experiments on the dual fluorescence of phenylpyrrole (PP) and pyrrolobenzonitrile (PBN) in supersonic jets and in cryogenic matrixes are analyzed. The structures of the 1:1 clusters are calculated using ab initio, density functional theory (DFF) and molecular mechanics (MM) methods. In these calculations, the structures of PP and PBN in the ground state and in two possible minima on the charge-transfer excited state are taken from a recent theoretical analysis. The structures of PP and PBN clusters with a larger number of acetonitrile molecules are also calculated using the molecular mechanics method. It is shown that the fact that small PPAN and PBN:AN clusters do not exhibit any charge-transfer (CT) type emission, whereas for PBN:AN(n) clusters (n >= 4) CT emission is observed, can be understood on the basis of the calculated structures. The trapping of PP and of PBN in an argon matrix (neat and doped with acetonitrile) is simulated by a molecular dynamics procedure. The observation of locally excited (LE) fluorescence only from PP in neat argon, whereas from argon-trapped PBN both CT and LE emission bands are observed, is readily understood on the basis of these simulations. Moreover, the appearance of CT emission from PP-doped argon matrixes when acetonitrile is added is also explained, as well as the relatively small spectral shift observed upon addition of acetonitrile to PBN-doped argon matrixes.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | INTRAMOLECULAR CHARGE-TRANSFER; MOLECULAR-DYNAMICS SIMULATIONS; EXCITED-STATE; VIBRATIONAL DYNAMICS; N-PHENYLPYRROLES; FLUORESCENCE; SPECTRA; JET; PYRROLOBENZONITRILE; PYRROLE; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Molecular Spectroscopy and Photochemistry) > Prof. Dr. Bernhard Dick |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 May 2021 04:59 |
| Last Modified: | 14 May 2021 04:59 |
| URI: | https://pred.uni-regensburg.de/id/eprint/36140 |
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