Comparison of frozen-density embedding and discrete reaction field solvent models for molecular properties

Christoph R. Jacob, Johannes Neugebauer, Lasse Jensen, Lucas Visscher

Research output: Contribution to journalArticle

67 Citations (Scopus)

Abstract

We investigate the performance of two discrete solvent models in connection with density functional theory (DFT) for the calculation of molecular properties. In our comparison we include the discrete reaction field (DRF) model, a combined quantum mechanics and molecular mechanics (QM/MM) model using a polarizable force field, and the frozen-density embedding (FDE) scheme. We employ these solvent models for ground state properties (dipole and quadrupole moments) and response properties (electronic excitation energies and frequency-dependent polarizabilities) of a water molecule in the liquid phase. It is found that both solvent models agree for ground state properties, while there are significant differences in the description of response properties. The origin of these differences is analyzed in detail and it is found that they are mainly caused by a different description of the ground state molecular orbitals of the solute. In addition, for the calculation of the polarizabilities, the inclusion of the response of the solvent to the polarization of the solute becomes important. This effect is included in the DRF model, but is missing in the FDE scheme. A way of including it in FDE calculations of the polarizabilities using finite field calculations is demonstrated.

Original languageEnglish (US)
Pages (from-to)2349-2359
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume8
Issue number20
DOIs
StatePublished - May 18 2006

Fingerprint

molecular properties
embedding
Ground state
ground state
solutes
Molecular mechanics
Excitation energy
Quantum theory
Molecular orbitals
Electronic properties
field theory (physics)
Density functional theory
quantum mechanics
molecular orbitals
liquid phases
dipole moments
quadrupoles
inclusions
Polarization
density functional theory

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Jacob, Christoph R. ; Neugebauer, Johannes ; Jensen, Lasse ; Visscher, Lucas. / Comparison of frozen-density embedding and discrete reaction field solvent models for molecular properties. In: Physical Chemistry Chemical Physics. 2006 ; Vol. 8, No. 20. pp. 2349-2359.
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Comparison of frozen-density embedding and discrete reaction field solvent models for molecular properties. / Jacob, Christoph R.; Neugebauer, Johannes; Jensen, Lasse; Visscher, Lucas.

In: Physical Chemistry Chemical Physics, Vol. 8, No. 20, 18.05.2006, p. 2349-2359.

Research output: Contribution to journalArticle

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