Non-empirical exchange-correlation parameterizations based on exact conditions from correlated orbital theory

The Journal of Chemical Physics
Roberto Luiz A Haiduke, Rodney J Bartlett

Abstract

Some of the exact conditions provided by the correlated orbital theory are employed to propose new non-empirical parameterizations for exchange-correlation functionals from Density Functional Theory (DFT). This reparameterization process is based on range-separated functionals with 100% exact exchange for long-range interelectronic interactions. The functionals developed here, CAM-QTP-02 and LC-QTP, show mitigated self-interaction error, correctly predict vertical ionization potentials as the negative of eigenvalues for occupied orbitals, and provide nice excitation energies, even for challenging charge-transfer excited states. Moreover, some improvements are observed for reaction barrier heights with respect to the other functionals belonging to the quantum theory project (QTP) family. Finally, the most important achievement of these new functionals is an excellent description of vertical electron affinities (EAs) of atoms and molecules as the negative of appropriate virtual orbital eigenvalues. In this case, the mean absolute deviations for EAs in molecules are smaller than 0.10 eV, showing that physical interpretation can indeed be ascribed to some unoccupied orbitals from DFT.

References

Jul 23, 2004·The Journal of Chemical Physics·Yoshihiro TawadaKimihiko Hirao
Aug 27, 2005·The Journal of Chemical Physics·Rodney J BartlettIgor V Schweigert
Sep 27, 2006·The Journal of Chemical Physics·Igor V SchweigertRodney J Bartlett
Dec 6, 2006·The Journal of Chemical Physics·Paula Mori-SánchezWeitao Yang
Apr 7, 2007·The Journal of Chemical Physics·Kirk A PetersonHermann Stoll
Apr 13, 2007·Journal of Chemical Information and Modeling·Karen L SchuchardtTheresa L Windus
May 26, 2007·The Journal of Chemical Physics·Aron J CohenWeitao Yang
Oct 24, 2007·The Journal of Chemical Physics·Ireneusz GrabowskiRodney J Bartlett
Jul 28, 2016·The Journal of Chemical Physics·Yifan Jin, Rodney J Bartlett
Oct 27, 2016·The Journal of Chemical Physics·Szymon ŚmigaJulien Toulouse
Jan 23, 2017·The Journal of Chemical Physics·Duminda S RanasingheRodney J Bartlett

❮ Previous
Next ❯

Citations

Nov 5, 2019·The Journal of Chemical Physics·Rodney J Bartlett
Oct 8, 2018·The Journal of Chemical Physics·Roberto Luiz Andrade Haiduke, Rodney J Bartlett
Aug 24, 2020·The Journal of Chemical Physics·J V Ortiz
Feb 19, 2021·Journal of Chemical Theory and Computation·Susi LehtolaDage Sundholm
Feb 21, 2021·The Journal of Chemical Physics·Rodrigo A MendesRodney J Bartlett
May 21, 2021·Journal of Computational Chemistry·Musen LiRoger D Amos
Jul 26, 2018·Chemical Reviews·Soumen GhoshDonald G Truhlar

❮ Previous
Next ❯

Related Concepts

Related Feeds

Adhesion Molecules in Health and Disease

Cell adhesion molecules are a subset of cell adhesion proteins located on the cell surface involved in binding with other cells or with the extracellular matrix in the process called cell adhesion. In essence, cell adhesion molecules help cells stick to each other and to their surroundings. Cell adhesion is a crucial component in maintaining tissue structure and function. Discover the latest research on adhesion molecule and their role in health and disease here.