Affiliation:
1. Department of Chemistry, The Johns Hopkins University , Baltimore, Maryland 21218, USA
Abstract
A first implementation of analytic gradients for spinor-based relativistic equation-of-motion coupled-cluster singles and doubles method using an exact two-component Hamiltonian augmented with atomic mean-field spin–orbit integrals is reported. To demonstrate its applicability, we present calculations of equilibrium structures and harmonic vibrational frequencies for the electronic ground and excited states of the radium mono-amide molecule (RaNH2) and the radium mono-methoxide molecule (RaOCH3). Spin–orbit coupling is shown to quench Jahn–Teller effects in the first excited state of RaOCH3, resulting in a C3v equilibrium structure. The calculations also show that the radium atoms in these molecules serve as efficient optical cycling centers.
Funder
U.S. Department of Energy
Subject
Physical and Theoretical Chemistry,General Physics and Astronomy