Title: Extending density functional embedding theory for covalently bonded systems

Abstract

Quantum embedding theory aims to provide an efficient solution to obtain accurate electronic energies for systems too large for full-scale, high-level quantum calculations. It adopts a hierarchical approach that divides the total system into a small embedded region and a larger environment, using different levels of theory to describe each part. Previously, we developed a density-based quantum embedding theory called density functional embedding theory (DFET), which achieved considerable success in metals and semiconductors. In this work, we extend DFET into a density-matrix–based nonlocal form, enabling DFET to study the stronger quantum couplings between covalently bonded subsystems. We name this theory density-matrix functional embedding theory (DMFET), and we demonstrate its performance in several test examples that resemble various real applications in both chemistry and biochemistry. DMFET gives excellent results in all cases tested thus far, including predicting isomerization energies, proton transfer energies, and highest occupied molecular orbital–lowest unoccupied molecular orbital gaps for local chromophores. Here, we show that DMFET systematically improves the quality of the results compared with the widely used state-of-the-art methods, such as the simple capped cluster model or the widely used ONIOM method.

Authors:

Yu, Kuang ^[1]; Carter, Emily A.  ^[2]

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• Search DOE PAGES for ORCID "0000-0001-7330-7554"

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+ Show Author Affiliations

1. Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544-5263,
2. School of Engineering and Applied Science, Princeton University, Princeton, NJ 08544-5263

Publication Date:

Mon Dec 04 00:00:00 EST 2017

Research Org.:

Princeton Univ., NJ (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1411118

Alternate Identifier(s):

OSTI ID: 1527122

Grant/Contract Number:  

SC0002120

Resource Type:

Published Article

Journal Name:

Proceedings of the National Academy of Sciences of the United States of America

Additional Journal Information:

Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 114 Journal Issue: 51; Journal ID: ISSN 0027-8424

Publisher:

Proceedings of the National Academy of Sciences

Country of Publication:

United States

Language:

English

Subject:

42 ENGINEERING