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Coupled cluster and density functional theory studies of the vibrational contribution to the optical rotation of (S)-propylene oxide

Kongsted, J ; Pedersen, Thomas LU ; Jensen, L ; Hansen, AE and Mikkelsen, KV (2006) In Journal of the American Chemical Society 128(3). p.976-982
Abstract
In a previous study (Chemical Physics Letters 2005, 401, 385) we computed the optical rotatory dispersion of (S)-propylene oxide in gas phase and solution using the hierarchy of coupled cluster models CCS, CC2, CCSD, and CC3. Even for the highly correlated CC3 model combined with a flexible basis set, the theoretical gas-phase specific rotation at 355 nm was found to be negative in contrast to the experimental result. We argued that vibrational contributions could be crucial for obtaining a complete understanding of the experimental result. Here, we show that this indeed is the case by using coupled cluster models and density functional theory methods to calculate the vibrational contributions to the gas-phase specific rotation at 355,... (More)
In a previous study (Chemical Physics Letters 2005, 401, 385) we computed the optical rotatory dispersion of (S)-propylene oxide in gas phase and solution using the hierarchy of coupled cluster models CCS, CC2, CCSD, and CC3. Even for the highly correlated CC3 model combined with a flexible basis set, the theoretical gas-phase specific rotation at 355 nm was found to be negative in contrast to the experimental result. We argued that vibrational contributions could be crucial for obtaining a complete understanding of the experimental result. Here, we show that this indeed is the case by using coupled cluster models and density functional theory methods to calculate the vibrational contributions to the gas-phase specific rotation at 355, 589.3, and 633 nm. While density functional theory (B3LYP and SAOP functionals) overestimates the specific rotation at 355 nm by approximately 1 order of magnitude and yields an incorrect sign at 589.3 and 633 nm, the coupled cluster results are in excellent agreement with the experimentally measured optical rotations. We find that all vibrational modes contribute significantly to the optical rotation and that temperature effects must be taken into account. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
128
issue
3
pages
976 - 982
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:16417389
  • wos:000234815000063
  • scopus:31444441389
  • pmid:16417389
ISSN
1520-5126
DOI
10.1021/ja056611e
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
b810883c-6b11-4854-8388-7f1549d8adcf (old id 419748)
date added to LUP
2016-04-01 17:04:38
date last changed
2021-05-18 02:32:52
@article{b810883c-6b11-4854-8388-7f1549d8adcf,
  abstract     = {In a previous study (Chemical Physics Letters 2005, 401, 385) we computed the optical rotatory dispersion of (S)-propylene oxide in gas phase and solution using the hierarchy of coupled cluster models CCS, CC2, CCSD, and CC3. Even for the highly correlated CC3 model combined with a flexible basis set, the theoretical gas-phase specific rotation at 355 nm was found to be negative in contrast to the experimental result. We argued that vibrational contributions could be crucial for obtaining a complete understanding of the experimental result. Here, we show that this indeed is the case by using coupled cluster models and density functional theory methods to calculate the vibrational contributions to the gas-phase specific rotation at 355, 589.3, and 633 nm. While density functional theory (B3LYP and SAOP functionals) overestimates the specific rotation at 355 nm by approximately 1 order of magnitude and yields an incorrect sign at 589.3 and 633 nm, the coupled cluster results are in excellent agreement with the experimentally measured optical rotations. We find that all vibrational modes contribute significantly to the optical rotation and that temperature effects must be taken into account.},
  author       = {Kongsted, J and Pedersen, Thomas and Jensen, L and Hansen, AE and Mikkelsen, KV},
  issn         = {1520-5126},
  language     = {eng},
  number       = {3},
  pages        = {976--982},
  publisher    = {The American Chemical Society (ACS)},
  series       = {Journal of the American Chemical Society},
  title        = {Coupled cluster and density functional theory studies of the vibrational contribution to the optical rotation of (S)-propylene oxide},
  url          = {http://dx.doi.org/10.1021/ja056611e},
  doi          = {10.1021/ja056611e},
  volume       = {128},
  year         = {2006},
}