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Solvent effects on NMR isotropic shielding constants. A comparison between explicit polarizable discrete and continuum approaches

Aidas, Kestutis; Mogelhoj, Andreas; Kjaer, Hanna; Nielsen, Christian B.; Mikkelsen, Kurt V.; Ruud, Kenneth; Christiansen, Ove and Kongsted, Jacob LU (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)
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organization
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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
external identifiers
  • wos:000246569300011
  • scopus:34250314092
ISSN
1520-5215
DOI
10.1021/jp068693e
language
English
LU publication?
yes
id
c115b6bf-8737-43f6-844e-77f55f715242 (old id 663384)
date added to LUP
2007-12-11 13:28:13
date last changed
2016-09-20 03:53:57
@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},
  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},
  volume       = {111},
  year         = {2007},
}