Title: Self-interaction corrected density functional calculations of molecular Rydberg states

A method is presented for calculating the wave function and energy of Rydberg excited states of molecules. A good estimate of the Rydberg state orbital is obtained using ground state density functional theory including Perdew-Zunger self-interaction correction and an optimized effective potential. The total energy of the excited molecule is obtained using the Delta Self-Consistent Field method where an electron is removed from the highest occupied orbital and placed in the Rydberg orbital. Results are presented for the first few Rydberg states of NH{sub 3}, H{sub 2}O, H{sub 2}CO, C{sub 2}H{sub 4}, and N(CH{sub 3}){sub 3}. The mean absolute error in the energy of the 33 molecular Rydberg states presented here is 0.18 eV. The orbitals are represented on a real space grid, avoiding the dependence on diffuse atomic basis sets. As in standard density functional theory calculations, the computational effort scales as NM{sup 2} where N is the number of orbitals and M is the number of grid points included in the calculation. Due to the slow scaling of the computational effort with system size and the high level of parallelism in the real space grid approach, the method presented here makes it possible to estimate Rydberg electron bindingmore » energy in large molecules.« less

Science Institute of the University of Iceland, 107 Reykjavík (Iceland)

Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States)

(Iceland)

Publication Date:

OSTI Identifier:

22251425

Resource Type:

Journal Article

Resource Relation:

Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 19; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)