Coupled cluster and density functional theory studies of the vibrational contribution to the optical rotation of (S)-propylene oxide
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/419748
- author
- Kongsted, J ; Pedersen, Thomas LU ; Jensen, L ; Hansen, AE and Mikkelsen, KV
- organization
- publishing date
- 2006
- 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
- 2023-01-05 05:00:29
@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}},
}