Back to Search
Start Over
Orbital-free embedding applied to the calculation of induced dipole moments in CO2...X (X=He, Ne, Ar, Kr, Xe, Hg) van der Waals complexes.
- Source :
-
Journal of Chemical Physics . 11/1/2005, Vol. 123 Issue 17, p174104. 11p. 6 Charts. - Publication Year :
- 2005
-
Abstract
- The orbital-free frozen-density embedding scheme within density-functional theory [T. A. Wesolowski and A. Warshel, J. Phys. Chem. 97, 8050 (1993)] is applied to the calculation of induced dipole moments of the van der Waals complexes CO2...X (X=He, Ne, Ar, Kr, Xe, Hg). The accuracy of the embedding scheme is investigated by comparing to the results of supermolecule Kohn-Sham density-functional theory calculations. The influence of the basis set and the consequences of using orbital-dependent approximations to the exchange-correlation potential in embedding calculations are examined. It is found that in supermolecular Kohn-Sham density-functional calculations, different common approximations to the exchange-correlation potential are not able to describe the induced dipole moments correctly and the reasons for this failure are analyzed. It is shown that the orbital-free embedding scheme is a useful tool for applying different approximations to the exchange-correlation potential in different subsystems and that a physically guided choice of approximations for the different subsystems improves the calculated dipole moments significantly. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 123
- Issue :
- 17
- Database :
- Academic Search Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 18795679
- Full Text :
- https://doi.org/10.1063/1.2107567