Spectroscopic determination of the vibrational potential energy surface and conformation of 1,3-benzodioxole in its S-1(pi,pi*) excited state. The effect of the electronic excitation on the anomeric effect
- Authors
- Laane, Jaan; Bondoc, Eugene; Sakurai, Sachie; Morris, Kevin; Meinander, Niklas; Choo, Jaebum
- Issue Date
- Mar-2000
- Publisher
- AMER CHEMICAL SOC
- Citation
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.122, no.11, pp 2628 - 2634
- Pages
- 7
- Journal Title
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- Volume
- 122
- Number
- 11
- Start Page
- 2628
- End Page
- 2634
- URI
- https://scholarworks.bwise.kr/cau/handle/2019.sw.cau/47374
- DOI
- 10.1021/ja9938128
- ISSN
- 0002-7863
1520-5126
- Abstract
- The electronic absorption spectra and the laser-induced fluorescence spectra of supersonic-jet-cooled 1,3-benzodioxole molecules have been investigated to map out the vibronic energy levels in the S-1(pi,pi*), electronic excited state. These were used to determine a two-dimensional potential energy surface in terms of the ring-puckering and ring-flapping vibrational coordinates, and the molecule was found to be puckered with a dihedral angle of 22 degrees. The barrier to planarity in the excited state is 264 cm(-1) (3.16 kJ/mol) as compared to 164 cm(-1) (1.96 kJ/mol) in the ground state. This increase is attributed to reduced suppression of the anomeric effect by the benzene ring resulting from decreased pi bonding character in the S-1(pi,pi*) state. As expected, the motion along the flapping coordinate is governed by a more shallow potential energy well. Ab initio calculations carried out for both the ground and excited states support the experimental conclusions.
- Files in This Item
-
- Appears in
Collections - College of Natural Sciences > Department of Chemistry > 1. Journal Articles
Items in ScholarWorks are protected by copyright, with all rights reserved, unless otherwise indicated.