A reinterpretation of the electronic spectrum of pyrrole: a quantum dynamics study.
J Chem Phys
; 140(3): 034317, 2014 Jan 21.
Article
em En
| MEDLINE
| ID: mdl-25669389
ABSTRACT
The first band in the electronic spectrum of pyrrole is calculated from wavepacket propagations performed using the MCTDH method. To do so, two model Hamiltonians are constructed to describe seven low-lying excited electronic states of pyrrole. These Hamiltonians are based on the vibronic coupling model, and are parameterised via fitting to extensive CASPT2 and EOM-CCSD calculations. A detailed analysis of the structure of pyrrole's electronic spectrum in the range 5.5 to 6.5 eV is made. The role of intensity borrowing from transitions to ππ(*) states by lower-lying 3s and 3p Rydberg states is assessed, and reassignments of much of the spectrum are subsequently made which indicate that most of the states in the spectrum are predominantly Rydberg in character. The resulting conclusions drawn serve to highlight the limitations of assignments based on the matching of calculated vertical excitation energies and the positions of peak maxima observed in electronic spectra.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Chem Phys
Ano de publicação:
2014
Tipo de documento:
Article
País de afiliação:
Reino Unido