Code that goes with extent of violation index calculations for molecules in W4-11 and G2RC datasets. Running instructions are present in both folders (W4-11 and G2RC).
Code for the simple linear regression experiment is also available (Regression_Exp).
Paper citation: @article{https://doi.org/10.1002/jcc.70005, author = {Khanna, Vaibhav and Kanungo, Bikash and Gavini, Vikram and Tewari, Ambuj and Zimmerman, Paul M.}, title = {Examining the Impact of Local Constraint Violations on Energy Computations in DFT}, journal = {Journal of Computational Chemistry}, volume = {46}, number = {1}, pages = {e70005}, keywords = {exact conditions, exchange-correlation (XC) functionals, extent of violation index (EVI), local constraints density functional theory (DFT)}, doi = {https://doi.org/10.1002/jcc.70005}, url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/jcc.70005}, eprint = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/jcc.70005}, note = {e70005 JCC-24-0503.R1}, abstract = {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.}, year = {2025} }