Jump to main content
Jump to site search
SCHEDULED MAINTENANCE Close the message box

Maintenance work is planned for Monday 16 August 2021 from 07:00 to 23:59 (BST).

Website performance may be temporarily affected and you may not be able to access some PDFs or images. If this does happen, refreshing your web browser should resolve the issue. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 36, 2010

Intramolecular competition in the photodissociation of C3D3 radicals at 248 and 193 nm

Author affiliations

Abstract

Motivated by recent experimental work, a theoretical study of the photodissociation of perdeuterated propargyl (D2CCD) and propynyl (D3CCC) radicals has been carried out, focusing on the C–C bond cleavage and D2 loss channels. High-level ab initio calculations were carried out, and RRKM rate constants were calculated for isomerization and dissociation pathways. The resulting reaction barriers, microcanonical rate constants and product branching ratios are consistent with the experimental findings, supporting the overall mechanism of internal conversion followed by statistical dissociation on the ground state surface. We found loose transition states and very low exit barriers for two of the C–C bond cleavage channels and an additional CD2 + CCD channel, which had not been reported previously. Our results probe the extent of propargyl and propynyl isomerization prior to dissociation at 248 and 193 nm and deliver a comprehensive picture of all ongoing molecular dynamics.

Graphical abstract: Intramolecular competition in the photodissociation of C3D3 radicals at 248 and 193 nm

Supplementary files

Article information


Submitted
28 Apr 2010
Accepted
06 Jul 2010
First published
16 Aug 2010

Phys. Chem. Chem. Phys., 2010,12, 10714-10722
Article type
Paper

Intramolecular competition in the photodissociation of C3D3 radicals at 248 and 193 nm

L. Castiglioni, S. Vukovic, P. E. Crider, W. A. Lester and D. M. Neumark, Phys. Chem. Chem. Phys., 2010, 12, 10714 DOI: 10.1039/C0CP00380H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements