We analyze the accuracy of the frozen density embedding (FDE) method, with hybrid and orbital-dependent exchange-correlation functionals, for the calculation of the total interaction energies of weakly interacting systems. Our investigation is motivated by the fact that these approaches require, in addition to the non-additive kinetic energy approximation, also approximate non-additive exact-exchange energies. Despite this further approximation, we find that the hybrid/orbital-dependent FDE approaches can reproduce the total energies with the same accuracy (about 1 mHa) as the one of conventional semi-local functionals. In many cases, thanks to error cancellation effects, hybrid/orbital-dependent approaches yield even the smallest error. A detailed energy-decomposition investigation is presented. Finally, the Becke-exchange functional is found to reproduce accurately the non-additive exact-exchange energies also for non-equilibrium geometries. These performances are rationalized in terms of a reduced-gradient decomposition of the non-additive exchange energy.
Skip Nav Destination
Article navigation
7 July 2012
Research Article|
July 02 2012
On the accuracy of frozen density embedding calculations with hybrid and orbital-dependent functionals for non-bonded interaction energies
S. Laricchia;
S. Laricchia
1Center for Biomolecular Nanotechnologies @UNILE,
Istituto Italiano di Tecnologia (IIT)
, Via Barsanti, 73010 Arnesano (LE), Italy
Search for other works by this author on:
E. Fabiano;
E. Fabiano
2National Nanotechnology Laboratory (NNL),
Istituto Nanoscienze-CNR
, Via per Arnesano 16, 73100 Lecce, Italy
Search for other works by this author on:
F. Della Sala
F. Della Sala
a)
1Center for Biomolecular Nanotechnologies @UNILE,
Istituto Italiano di Tecnologia (IIT)
, Via Barsanti, 73010 Arnesano (LE), Italy
2National Nanotechnology Laboratory (NNL),
Istituto Nanoscienze-CNR
, Via per Arnesano 16, 73100 Lecce, Italy
Search for other works by this author on:
a)
Author to whom correspondence should be addressed. Electronic mail: [email protected].
J. Chem. Phys. 137, 014102 (2012)
Article history
Received:
April 22 2012
Accepted:
June 08 2012
Citation
S. Laricchia, E. Fabiano, F. Della Sala; On the accuracy of frozen density embedding calculations with hybrid and orbital-dependent functionals for non-bonded interaction energies. J. Chem. Phys. 7 July 2012; 137 (1): 014102. https://doi.org/10.1063/1.4730748
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
Semilocal and hybrid density embedding calculations of ground-state charge-transfer complexes
J. Chem. Phys. (March 2013)
Apparent violation of the sum rule for exchange-correlation charges by generalized gradient approximations
J. Chem. Phys. (October 2013)
Subsystem density functional theory with meta-generalized gradient approximation exchange-correlation functionals
J. Chem. Phys. (April 2015)
Charge-constrained auxiliary-density-matrix methods for the Hartree–Fock exchange contribution
J. Chem. Phys. (September 2014)