Dyson Orbitals Within Equation-Of-Motion Coupled-Cluster Formalism for Wave Function Analysis and Cross Section Calculations

Physical and Analytical Chemistry Seminar

Lecturer: Prof. Anna Krylov

20 Oct 2015 @ 15:30

Location: Faculty Seminar Room

Abstract: Interpretation of spectroscopic measurements of reaction intermediates requires cross sections for photoionization/detachment or electronic excitation. Cross sections can be used to assign features in photoelectron spectra, photoelectron efficiency curves, to explain angular distributions of photoelectrons, and more. The key quantity for computing photoionization cross sections is the so-called Dyson orbital. I will introduce the formalism for Dyson orbitals calculations within equation-of-motion coupled-cluster theory and present our recent results on modeling absolute photoionization cross sections. Dyson orbitals are also very important for analyzing the character of different states in electronically excited and open-shell species, including bound and unbound (metastable) electronic states. Their utility will be illustrated by the examples.
[1] C.M. Oana and A.I. Krylov, Dyson orbitals for ionization from the ground and electronically excited states within equation-of-motion coupled-cluster formalism: Theory, implementation, and examples, J. Chem. Phys. 127, 234106 (2007).
[2] A.I. Krylov, Equation-of-motion coupled-cluster methods for open-shell and electronically excited species: The hitchhiker’s guide to Fock space, Annu. Rev. Phys. Chem. 59, 433 (2008).