Can Density Matrix Embedding Theory with the Complete Activate Space Self-Consistent Field Solver Describe Single and Double Bond Breaking in Molecular Systems?

Hung Q. Pham, Varinia Bernales, Laura Gagliardi

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

Density matrix embedding theory (DMET) [Phys. Rev. Lett. 2012, 109, 186404] has been demonstrated as an efficient wave-function-based embedding method to treat extended systems. Despite its success in many quantum lattice models, the extension of DMET to real chemical systems has been tested only on selected cases. Herein, we introduce the use of the complete active space self-consistent field (CASSCF) method as a correlated impurity solver for DMET, leading to a method called CAS-DMET. We test its performance in describing the dissociation of H-H single bonds in a H10 ring model system and an N=N double bond in azomethane (CH3-N=N-CH3) and pentyldiazene (CH3(CH2)4-N=NH). We find that the performance of CAS-DMET is comparable to CASSCF with different active space choices when single-embedding DMET corresponding to only one embedding problem for the system is used. When multiple embedding problems are used for the system, the CAS-DMET is in good agreement with CASSCF for the geometries around the equilibrium, but not in equal agreement at bond dissociation.

Original languageEnglish (US)
Pages (from-to)1960-1968
Number of pages9
JournalJournal of Chemical Theory and Computation
Volume14
Issue number4
DOIs
StatePublished - Apr 10 2018

Bibliographical note

Funding Information:
We thank Gustavo Scuseria, Matthew Hermes, Christopher J. Cramer, and Donald G. Truhlar for useful discussion. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award No. DEFG02-12ER16362.

Publisher Copyright:
© 2018 American Chemical Society.

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