Density functional theory study of 1,2-dioxetanone decomposition in condensed phase

• Type: Article in International Scientific Journal
• Date: 2012

Authors

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

Journal

Title: Journal of Computational Chemistry

Vol. 33

Pages: 2118-2123

ISSN: 0192-8651

Publisher: Wiley-Blackwell

Indexing

ISI Web of Knowledge - 15 Citations

Scopus - 14 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-002-4GX

DOI: 10.1002/jcc.22997

Abstract (EN): The decomposition of 1,2-dioxetanone into a CO2 molecule and into an excited state formaldehyde molecule was studied in condensed phase, using a density functional theory approach. Singlet and triplet ground and excited states were all included in the calculations. The calculations revealed a novel mechanism for the chemiluminescence of this compound. The triplet excitation can be explained by two intersystem crossings (ISCs) with the ground state, while the singlet excitation can be accounted by an ISC with the triplet state. The experimentally verified small excitation yield can then be explained by the presence of an energy barrier present in the potential energy surface of the triplet excited state, which will govern both triplet and singlet excitation. It was also found that the triplet ground state interacts with both the triplet excited and singlet ground states. A MPWB1K/mPWKCIS approach provided results in agreement with the existent literature. (c) 2012 Wiley Periodicals, Inc.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 6