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On the importance of vibrational contributions to small-angle optical rotation: Fluoro-oxirane in gas phase and solution.

Pedersen, Thomas LU ; Kongsted, Jacob LU ; Crawford, T Daniel and Ruud, Kenneth (2009) In Journal of Chemical Physics 130(3).
Abstract
The specific optical rotation of (S)-fluoro-oxirane in gas phase and solution is predicted using time-dependent density functional theory (B3LYP functional) and coupled cluster linear response theory. Upon vibrational averaging, the coupled cluster singles and doubles model predicts the gas phase specific optical rotation to be 8.1 degrees (dm g/cm(3))(-1) at 355 nm at room temperature. This is an order of magnitude smaller than the B3LYP result of 68.4 degrees (dm g/cm(3))(-1). The main source of this discrepancy is the electronic contribution at the equilibrium geometry. The effects of cyclohexane and acetonitrile solvents are calculated for both the electronic and vibrational contributions with the B3LYP functional. The specific optical... (More)
The specific optical rotation of (S)-fluoro-oxirane in gas phase and solution is predicted using time-dependent density functional theory (B3LYP functional) and coupled cluster linear response theory. Upon vibrational averaging, the coupled cluster singles and doubles model predicts the gas phase specific optical rotation to be 8.1 degrees (dm g/cm(3))(-1) at 355 nm at room temperature. This is an order of magnitude smaller than the B3LYP result of 68.4 degrees (dm g/cm(3))(-1). The main source of this discrepancy is the electronic contribution at the equilibrium geometry. The effects of cyclohexane and acetonitrile solvents are calculated for both the electronic and vibrational contributions with the B3LYP functional. The specific optical rotation is estimated to change significantly depending on the polarity of the solvent, increasing in cyclohexane and decreasing in acetonitrile. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
130
issue
3
publisher
American Institute of Physics
external identifiers
  • wos:000262671700024
  • pmid:19173524
  • scopus:58749116459
ISSN
0021-9606
DOI
10.1063/1.3054301
language
English
LU publication?
yes
id
d7ad2d6f-406d-4d24-adfc-d98eb15e7e9b (old id 1289223)
date added to LUP
2009-02-19 15:53:56
date last changed
2017-11-19 03:31:02
@article{d7ad2d6f-406d-4d24-adfc-d98eb15e7e9b,
  abstract     = {The specific optical rotation of (S)-fluoro-oxirane in gas phase and solution is predicted using time-dependent density functional theory (B3LYP functional) and coupled cluster linear response theory. Upon vibrational averaging, the coupled cluster singles and doubles model predicts the gas phase specific optical rotation to be 8.1 degrees (dm g/cm(3))(-1) at 355 nm at room temperature. This is an order of magnitude smaller than the B3LYP result of 68.4 degrees (dm g/cm(3))(-1). The main source of this discrepancy is the electronic contribution at the equilibrium geometry. The effects of cyclohexane and acetonitrile solvents are calculated for both the electronic and vibrational contributions with the B3LYP functional. The specific optical rotation is estimated to change significantly depending on the polarity of the solvent, increasing in cyclohexane and decreasing in acetonitrile.},
  articleno    = {034310},
  author       = {Pedersen, Thomas and Kongsted, Jacob and Crawford, T Daniel and Ruud, Kenneth},
  issn         = {0021-9606},
  language     = {eng},
  number       = {3},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {On the importance of vibrational contributions to small-angle optical rotation: Fluoro-oxirane in gas phase and solution.},
  url          = {http://dx.doi.org/10.1063/1.3054301},
  volume       = {130},
  year         = {2009},
}