New Coupled-cluster and Density Functional Theory for the Description of Molecular Electronic Structure and Spectra
Abstract
A three year renewal of our AFOSR grant is requested to cover several new developments in theory applied to Air Force problems. These include core ionization and excitation spectra, potential energy surfaces for strongly correlated systems, doubly excited states in equation-of-motion coupled-cluster (CC) theory (EOM-CC), and the time-dependent CC for the direct prediction of molecular spectra from the core to the valence to high lying Rydberg states. All these objectives tie closely to our development of correlated orbital theory (COT) that is meant to replace standard MO theory by a quantitative form that associates each electron in an occupied orbital to its eigenvalue that would be its experimentally observed ionization potential in the exact limit. The COT enables one to transition to Kohn-Sham density functional theory (DFT) to define a minimally parameterized new family of range-separated DFT functionals, CAM- QTP(00), QTP(01), and QTP(02), geared at resolving the errors in KS-DFT applications summarized in our Devil’s Triangle, figure. These solve the problem of the incorrect one-particle spectrum that pertains to all other KS-DFT functionals, charge-transfer excited states in DFT and TD-DFT, provides accurate densities and activation barriers, gives excellent fully relaxed core ionizations and excitation spectra, and mitigates the pervasive self-interaction problem of KS-DFT. Future efforts will focus on the treatment of response properties in COT and its QTP functional approximations, consequences in ligand field theory with emphasis on transition metal complexes, and application of quantitative Frontier MO theory for reactions.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Feb 29, 2024
- Source ID
- FA95502310118
Entities
People
- Rodney J. Bartlett
Organizations
- Air Force Office of Scientific Research
- United States Air Force
- University of Florida