Reparameterization of exchange-correlation functionals based on the Bartlett's ionization potential theorem

• Grant number: 16/18704-2
• Support Opportunities: Scholarships abroad - Research
• Start date: August 01, 2017
• End date: March 31, 2018
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Roberto Luiz Andrade Haiduke
• Grantee: Roberto Luiz Andrade Haiduke
• Host Investigator: Rodney J. Bartlett
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• Institution abroad: University of Florida, Gainesville (UF), United States

Abstract

Density Functional Theory (DFT) provides the most efficient way to access the electronic structure of moderate to large molecular systems. However, the performance of DFT is intrinsically related to the exchange-correlation functional chosen. Recently, exchange-correlation functionals have been developed by requiring the fulfillment of the Bartlett's ionization potential theorem and such proposal proved especially advantageous for Time-Dependent DFT (TD-DFT) calculations. Hence, the objective of this project is to apply the Bartlett's theorem in the reparameterization of hybrid, range-separated and/or double-hybrid functionals, which will be also evaluated by means of relativistic quantum chemistry calculations. Special emphasis will be devoted to the study of transition metal compounds. The key molecular properties employed to this end are ionization potentials (from both orbital eigenvalues and SCF calculations) and electronic excitation energies. Next, the resulting values of other quantities such as geometries, dipole moments, vibrational frequencies, reaction activation barriers, proton and electron affinities will also be analyzed. In addition, the electron densities provided by these functionals will be carefully scrutinized to identify the reparameterization effect over such a key property for DFT. In this case, the Quantum Theory of Atoms in Molecules formalism will be helpful to simplify the required electron density analyses, which will be focused on critical point characteristics of ground and excited electronic states. (AU)

Scientific publications

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

ANDRADE HAIDUKE, ROBERTO LUIZ; BARTLETT, RODNEY J.. Communication: Can excitation energies be obtained from orbital energies in a correlated orbital theory?. Journal of Chemical Physics, v. 149, n. 13, OCT 7 2018. (16/18704-2)

HAIDUKE, ROBERTO LUIZ A.; BARTLETT, RODNEY J.. Non-empirical exchange-correlation parameterizations based on exact conditions from correlated orbital theory. Journal of Chemical Physics, v. 148, n. 18, MAY 14 2018. (16/18704-2)