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Fragment-Based Local Coupled Cluster Embedding Approach for the Quantification and Analysis of Noncovalent Interactions: Exploring the Many-Body Expansion of the Local Coupled Cluster Energy
- Source :
- Journal of Chemical Theory and Computation
- Publication Year :
- 2021
- Publisher :
- American Chemical Society (ACS), 2021.
-
Abstract
- Herein, we introduce a fragment-based local coupled cluster embedding approach for the accurate quantification and analysis of noncovalent interactions in molecular aggregates. Our scheme combines two different expansions of the domain-based local pair natural orbital coupled cluster (DLPNO-CCSD(T)) energy: the many-body expansion (MBE) and the local energy decomposition (LED). The low-order terms in the MBE are initially computed in the presence of an environment that is treated at a low level of theory. Then, LED is used to decompose the energy of each term in the embedded MBE into additive fragment and fragment-pairwise contributions. This information is used to quantify the total energy of the system while providing at the same time in-depth insights into the nature and cooperativity of noncovalent interactions. Two different approaches are introduced and tested, in which the environment is treated at different levels of theory: the local coupled cluster in the Hartree-Fock (LCC-in-HF) method, in which the environment is treated at the HF level; and the electrostatically embedded local coupled cluster method (LCC-in-EE), in which the environment is replaced by point charges. Both schemes are designed to preserve as much as possible the accuracy of the parent local coupled cluster method for total energies, while being embarrassingly parallel and less memory intensive. These schemes appear to be particularly promising for the study of large and complex molecular aggregates at the coupled cluster level, such as condensed phase systems and protein-ligand interactions.
- Subjects :
- chemistry.chemical_classification
Physics
010304 chemical physics
Embarrassingly parallel
Phase (waves)
Cooperativity
01 natural sciences
Article
Computer Science Applications
Coupled cluster
chemistry
Fragment (logic)
0103 physical sciences
Non-covalent interactions
Embedding
Physical and Theoretical Chemistry
Biological system
Energy (signal processing)
Subjects
Details
- ISSN :
- 15499626 and 15499618
- Volume :
- 17
- Database :
- OpenAIRE
- Journal :
- Journal of Chemical Theory and Computation
- Accession number :
- edsair.doi.dedup.....ea62cd3d5f620e18a1f4af0c133a6b3e