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

• Type: Article in International Scientific Journal
• Date: 2013

Authors

da silva, lp (Author) Other; da silva, jcge (Author) FCUP

Journal

Title: ChemPhysChem

Vol. 14

Pages: 1071-1079

ISSN: 1439-4235

Publisher: Wiley-Blackwell

Indexing

ISI Web of Knowledge - 25 Citations

ISI Web of Science

Scopus - 26 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

CORDIS: Physical sciences > Chemistry

Other information

Authenticus ID: 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.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 9