Finite-Field Calculations of Transition Properties by the Fock Space Relativistic Coupled Cluster Method: Transitions between Different Fock Space Sectors

Abstract

Reliable information on transition matrix elements of various property operators between molecular electronic states is of crucial importance for predicting spectroscopic, electric, magnetic and radiative properties of molecules. The finite-field technique is a simple and rather accurate tool for evaluating transition matrix elements of first-order properties in the frames of the Fock space relativistic coupled cluster approach. We formulate and discuss the extension of this technique to the case of transitions between the electronic states associated with different sectors of the Fock space. Pilot applications to the evaluation of transition dipole moments between the closed-shell-like states (vacuum sector) and those dominated by single excitations of the Fermi vacuum (the $1h1p$ sector) in heavy atoms (Xe, Hg) and simple molecules of heavy element compounds (I${}_2$, TlF) are reported.

Ab initio relativistic treatment of the intercombination $a^3Π-X^1Σ^+$ Cameron system of the CO molecule

“…Transition dipole moments D ij between the electronic states ψ i , ψ j of CO were calculated with the help of the finite-field technique [37,38], using the approximate relation…”

“…It is worth noting that, in contrast with the complete-model-space case [37], the projections { ψi } are not directly obtained as eigenfunctions of the FS-RCC effective Hamiltonian. However, these eigenfunction can be readily transformed into { ψi }, using the "closed" (i. e. acting within L (0h0p+1h1p) ) part of the cluster operator [38].…”