Assessment of the performance of DFT functionals in the fulfillment of off-diagonal hypervirial relationships. Issue 28 (9th July 2021)

• Record Type: Journal Article
• Authors: Summa, Francesco F.; Monaco, Guglielmo; Lazzeretti, Paolo; Zanasi, Riccardo
• Is Part Of: Physical chemistry chemical physics. Volume 23:Issue 28(2021)
• Page Start: 15268
• Page End: 15274
• Publication Date: 2021-07-09
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp01298c
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Off-diagonal hypervirial relationships, combined with quantum mechanical sum rules of charge-current conservation, offer a way to test electronic excited-state transition energies and moments, which does not need any external reference. Abstract : Off-diagonal hypervirial relationships, combined with quantum mechanical sum rules of charge-current conservation, offer a way to test electronic excited-state transition energies and moments, which does not need any external reference. A number of fundamental relationships were recast into absolute deviations from zero, which have been used to assess the performance of some popular DFT functionals. Extended TD-DFT calculations have been carried out for a pool of molecules chosen for this purpose, adopting a large basis set to ensure high quality results. A partial agreement with previous benchmarks is observed.