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Title: Examining the Impact of Local Constraint Violations on Energy Computations in DFT

Journal Article · · Journal of Computational Chemistry
DOI: https://doi.org/10.1002/jcc.70005 · OSTI ID:2496764
ORCiD logo [1];  [2];  [3];  [4];  [1]
  1. Department of Chemistry University of Michigan Ann Arbor Michigan USA
  2. Department of Mechanical Engineering University of Michigan Ann Arbor Michigan USA
  3. Department of Mechanical Engineering University of Michigan Ann Arbor Michigan USA, Department of Materials Science &, Engineering University of Michigan Ann Arbor Michigan USA
  4. Department of Statistics University of Michigan Ann Arbor Michigan USA
+ Show Author Affiliations

ABSTRACT This work examines the impact of locally imposed constraints in Density Functional Theory (DFT). Using a metric referred to as the extent of violation index (EVI), we quantify how well exchange‐correlation functionals adhere to local constraints. Applying EVIs to a diverse set of molecules for GGA functionals reveals constraint violations, particularly for semi‐empirical functionals. We leverage EVIs to explore potential connections between these violations and errors in chemical properties. While no correlation is observed for atomization energies, a significant statistical correlation emerges between EVIs and total energies. Similarly, the analysis of reaction energies suggests weak positive correlations for specific constraints. However, definitive conclusions about error cancellation mechanisms cannot be made at this time. These observations revealed by EVIs may be useful for consideration when designing future generations of semilocal functionals.

Sponsoring Organization:
USDOE
OSTI ID:
2496764
Journal Information:
Journal of Computational Chemistry, Journal Name: Journal of Computational Chemistry Journal Issue: 1 Vol. 46; ISSN 0192-8651
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
United States
Language:
English

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