On the accuracy of frozen density embedding calculations with hybrid and orbital-dependent functionals for non-bonded interaction energies
| Autor: | S. Laricchia, Eduardo Fabiano, F. Della Sala |
|---|---|
| Rok vydání: | 2012 |
| Předmět: |
Physics
010304 chemical physics Exchange interaction General Physics and Astronomy subsystem dft Kinetic energy 01 natural sciences Error cancellation embedding Kinetics Computational chemistry Yield (chemistry) frozen-density embedding 0103 physical sciences Embedding Quantum Theory Thermodynamics Density functional theory Statistical physics Physical and Theoretical Chemistry Total energy fde 010306 general physics hybrid functionals |
| Zdroj: | The Journal of Chemical Physics Journal of chemical physics online 137 (2012): 014102. doi:10.1063/1.4730748 info:cnr-pdr/source/autori:S. Laricchia, E. Fabiano, F. Della Sala/titolo:On the accuracy of frozen density embedding calculations with hybrid and orbital-dependent functionals for non-bonded interaction energies/doi:10.1063%2F1.4730748/rivista:Journal of chemical physics online/anno:2012/pagina_da:014102/pagina_a:/intervallo_pagine:014102/volume:137 |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/1.4730748 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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