The effective relativistic coupling by asymptotic representation approach for molecules with multiple relativistic atoms

Abstract

The Effective Relativistic Coupling by Asymptotic Representation (ERCAR) approach is a method to generate fully coupled diabatic potential energy surfaces (PESs) including relativistic effects, especially spin–orbit coupling. The spin–orbit coupling of a full molecule is determined only by the atomic states of selected relativistically treated atoms. The full molecular coupling effect is obtained by a diabatization with respect to asymptotic states, resulting in the correct geometry dependence of the spin–orbit effect. The ERCAR approach has been developed over the last decade and initially only for molecules with a single relativistic atom. This work presents its extension to molecules with more than a single relativistic atom using the iodine molecule as a proof-of-principle example. The theory for the general multiple atomic ERCAR approach is given. In this case, the diabatic basis is defined at the asymptote where all relativistic atoms are separated from the remaining molecular fragment. The effective spin–orbit operator is then a sum of spin–orbit operators acting on isolated relativistic atoms. PESs for the iodine molecule are developed within the new approach and it is shown that the resulting fine structure states are in good agreement with spin–orbit ab initio calculations.