Interstate Crossing-Induced Chemiexcitation as the Reason for the Chemiluminescence of Dioxetanones

• Tipo: Artigo em Revista Científica Internacional
• Data: 2013

Autores

da silva, lp (Autor) Outra; da silva, jcge (Autor) FCUP

Revista

Título: ChemPhysChem

Vol. 14

Páginas: 1071-1079

ISSN: 1439-4235

Editora: Wiley-Blackwell

Indexação

ISI Web of Knowledge - 25 Citações

ISI Web of Science

Scopus - 26 Citações

Classificação Científica

FOS: Ciências exactas e naturais > Química

CORDIS: Ciências Físicas > Química

Outras Informações

ID Authenticus: P-005-1PF

DOI: 10.1002/cphc.201200872

Abstract (EN): The decomposition reaction of dimethyl-1,2-dioxetanone in dichloromethane was studied by using a DFT approach. The low efficiency of triplet and singlet excited-state formation was rationalised. A charge-transfer process was demonstrated to be involved in the chemiluminescence process. Present and previous results allow us to define an interstate crossing-induced chemiexcitation (ICIC) mechanism for the chemiluminescence of dioxetanones. Charge transfer is needed to reach a transition state, in the vicinity of which direct population of excited states is possible. The chemiexcitation process is then governed by singlet/triplet intersystem crossings. Structural modifications then modify the rate of these crossings and the singlet ground and excited-state interaction, thereby modulating the efficiency of this process and the spin of the resulting products.

Idioma: Inglês

Tipo (Avaliação Docente): Científica

Nº de páginas: 9