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https://hdl.handle.net/2440/17935
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Type: | Journal article |
Title: | The lowest-lying excited singlet and triplet electronic states of propanal: an ab initio molecular orbital investigation of the potential energy surfaces |
Author: | Buntine, M. Lee, J. Metha, G. |
Citation: | Physical Chemistry Chemical Physics, 2004; 6(4):688-696 |
Publisher: | Royal Soc Chemistry |
Issue Date: | 2004 |
ISSN: | 1463-9076 1463-9084 |
Statement of Responsibility: | Mark. A. Buntine, Chansik Lee and Gregory F. Metha |
Abstract: | This study explores the potential energy surfaces of the So, S₁ and T₁ states using ab initio theory to provide insight into the spectroscopy, photochemistry and reaction dynamics of propanal. Minima associated with the formyl potential energy coordinate in the S₁ and T₁ states are found to be ~60° out-of-phase with the So state. Furthermore, the excited states possess a pyramidal formyl carbon atom that leads to a double minimum at ±33° and ±49° for the S₁ and T₁ states, respectively. An exploration of the C–C dissociation coordinate on the T₁ surface, yielding the products CH₃CH₂ + CHO, shows that a three-fold potential due to the formyl torsion is still operational, resulting in three unique transition states that lead to dissociation. The lowest energy pathway to dissociation occurs at a barrier height of 4766 cm⁻¹ and the energy of the products is found to be 1017 cm⁻¹, relative to the T₁ global minimum. Consequently, a reverse barrier of 3749 cm⁻¹ is calculated. Parameters calculated for the lowest energy transition state geometry are distinctly different from structures inferred from experiment, which assumed an isotropic dissociation channel. |
Description: | Copyright © 2004 Royal Society of Chemistry |
DOI: | 10.1039/b313777e |
Published version: | http://www.rsc.org/Publishing/Journals/CP/article.asp?doi=b313777e |
Appears in Collections: | Aurora harvest 2 Chemistry publications Environment Institute publications |
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