Scientific article
English

Benchmark of the Extension of Frozen-Density Embedding Theory to Nonvariational Correlated Methods: The Embedded-MP2 Case

Published inJournal of chemical theory and computation, vol. 17, no. 7, p. 4049-4062
Publication date2021-06-17
First online date2021-06-17
Abstract

The extension of the frozen-density embedding theory for nonvariational methods [J. Chem. Theory Comput.2020,16, 6880] was utilized to evaluate intermolecular interaction energies for complexes in the Zhao–Truhlar basis set. In the applied method (FDET-MP2-FAT-LDA), the same auxiliary system is used to evaluate the correlation energy by means of the second-order Møller–Plesset perturbation theory (MP2), as in our previous work [J. Chem. Phys.2019,150, 121101]. Local density approximation is used for ExcTnadAB] in both cases. Additionally, the contribution to the energy due to the neglected correlation potential was evaluated and analyzed. The domain of applicability of the local density approximation for ExcTnadAB] was determined based on deviations from the interaction energies from the conventional MP2 calculations. The local density approximation for ExcTnadAB] performs well for hydrogen- or dipole-bound complexes. The relative errors in the interaction energy lie within 3–30%. While for charge-transfer complexes, this approximation fails consistently, and for other types of complexes, the performance of this approximation is not systematic. The sources of error are discussed in detail.

Keywords
  • Approximation
  • Electrical energy
  • Embedding
  • Energy
  • Interaction energies
Citation (ISO format)
SEN, Reena et al. Benchmark of the Extension of Frozen-Density Embedding Theory to Nonvariational Correlated Methods: The Embedded-MP2 Case. In: Journal of chemical theory and computation, 2021, vol. 17, n° 7, p. 4049–4062. doi: 10.1021/acs.jctc.1c00228
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Additional URL for this publicationhttps://pubs.acs.org/doi/10.1021/acs.jctc.1c00228
Journal ISSN1549-9618
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