Molecular Structure, Spectra and Reactions: The Development of New Theory, Its Implementations and Applications
Abstract
In the last four years of our work for AFOSR, we have done a number of things that build on our proof of an exact, correlated orbital theory as an effective one-particle theory. The idea is to provide coupled-cluster (CC) accuracy for molecular structure and spectra, but within a computational framework that exploits its one-particle character. This makes it possible to do much larger systems than can be done in traditional CC theory, even with our development of massively parallel computer programs like ACES 3 and 4. This effort also ties to CC theory, that has to converge to the correct answer in appropriate limits. COT has Kohn-Sham density functional theory (DFT) as a special case. Exploiting this connection has led to four new 'consistent' DFT functionals of the QTP family. Unlike conventional DFT1, they provide an accurate one-particle spectrum, solve the problem of charge-transfer excited states in KS-DFT, provide accurate densities and activation barriers, give excellent fully relaxed core ionizations and excitation spectra, and ameliorate the pervasive self-interaction problem of KS-DFT. Several further developments are anticipated, including their extension to infinite polymers and solids.
Document Details
- Document Type
- Technical Report
- Publication Date
- Oct 05, 2018
- Accession Number
- AD1061504
Entities
People
- Ajith Perera
- Rodney J. Bartlett
Organizations
- University of Florida