Solvent effects on NMR isotropic shielding constants. A comparison between explicit polarizable discrete and continuum approaches
(2007) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 111(20). p.4199-4210- Abstract
- The gas-to-aqueous solution shifts of the O-17 and C-13 NMR isotropic shielding constants for the carbonyl chromophore in formaldehyde and acetone are investigated. For the condensed-phase problem, we use the hybrid density functional theory/molecular mechanics approach in combination with a statistical averaging over an appropriate number of solute-solvent configurations extracted from classical molecular dynamics simulations. The PBE0 exchange-correlation functional and the 6-311++G(2d,2p) basis set are used for the calculation of the shielding constants. London atomic orbitals are employed to ensure gauge-origin independent results. The effects of the bulk solvent molecules are found to be crucial in order to calculate accurate... (More)
- The gas-to-aqueous solution shifts of the O-17 and C-13 NMR isotropic shielding constants for the carbonyl chromophore in formaldehyde and acetone are investigated. For the condensed-phase problem, we use the hybrid density functional theory/molecular mechanics approach in combination with a statistical averaging over an appropriate number of solute-solvent configurations extracted from classical molecular dynamics simulations. The PBE0 exchange-correlation functional and the 6-311++G(2d,2p) basis set are used for the calculation of the shielding constants. London atomic orbitals are employed to ensure gauge-origin independent results. The effects of the bulk solvent molecules are found to be crucial in order to calculate accurate solvation shifts of the shielding constants. Very good agreement between the computed and experimental solvation shifts is obtained for the shielding constants of acetone when a polarizable water potential is used. Supermolecular results based on geometry-optimized molecular structures are presented. We also compare the results obtained with the polarizable continuum model to the results obtained using explicit MM molecules to model the bulk solvent effect. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/663384
- author
- Aidas, Kestutis ; Mogelhoj, Andreas ; Kjaer, Hanna ; Nielsen, Christian B. ; Mikkelsen, Kurt V. ; Ruud, Kenneth ; Christiansen, Ove and Kongsted, Jacob LU
- organization
- publishing date
- 2007
- type
- Contribution to journal
- publication status
- published
- subject
- in
- The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
- volume
- 111
- issue
- 20
- pages
- 4199 - 4210
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000246569300011
- pmid:17474726
- scopus:84962432238
- ISSN
- 1520-5215
- DOI
- 10.1021/jp068693e
- 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
- c115b6bf-8737-43f6-844e-77f55f715242 (old id 663384)
- date added to LUP
- 2016-04-01 16:20:06
- date last changed
- 2023-04-08 02:39:54
@article{c115b6bf-8737-43f6-844e-77f55f715242,
abstract = {{The gas-to-aqueous solution shifts of the O-17 and C-13 NMR isotropic shielding constants for the carbonyl chromophore in formaldehyde and acetone are investigated. For the condensed-phase problem, we use the hybrid density functional theory/molecular mechanics approach in combination with a statistical averaging over an appropriate number of solute-solvent configurations extracted from classical molecular dynamics simulations. The PBE0 exchange-correlation functional and the 6-311++G(2d,2p) basis set are used for the calculation of the shielding constants. London atomic orbitals are employed to ensure gauge-origin independent results. The effects of the bulk solvent molecules are found to be crucial in order to calculate accurate solvation shifts of the shielding constants. Very good agreement between the computed and experimental solvation shifts is obtained for the shielding constants of acetone when a polarizable water potential is used. Supermolecular results based on geometry-optimized molecular structures are presented. We also compare the results obtained with the polarizable continuum model to the results obtained using explicit MM molecules to model the bulk solvent effect.}},
author = {{Aidas, Kestutis and Mogelhoj, Andreas and Kjaer, Hanna and Nielsen, Christian B. and Mikkelsen, Kurt V. and Ruud, Kenneth and Christiansen, Ove and Kongsted, Jacob}},
issn = {{1520-5215}},
language = {{eng}},
number = {{20}},
pages = {{4199--4210}},
publisher = {{The American Chemical Society (ACS)}},
series = {{The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory}},
title = {{Solvent effects on NMR isotropic shielding constants. A comparison between explicit polarizable discrete and continuum approaches}},
url = {{http://dx.doi.org/10.1021/jp068693e}},
doi = {{10.1021/jp068693e}},
volume = {{111}},
year = {{2007}},
}