How to Stay out of Trouble in RIXS Calculations Within the Equation-of-Motion Coupled-Cluster Damped Response Theory Framework? Safe Hitchhiking in the Excitation Manifold by Means of Core-Valence Separation
2019-08-14T14:17:38Z (GMT) by
We present a novel approach for computing resonant inelastic X-ray scattering (RIXS) cross sections within the equation-of-motion coupled-cluster (EOM-CC) framework. The approach is based on recasting the sum-over-state expressions for RIXS moments into a compact form by using damped response theory. Damped response formalism allows one to circumvent problems of divergent behavior of the response equation in the resonant regime. However, the convergence of response equations in the X-ray frequency range is often erratic due to the resonant nature of the virtual core-excited states embedded in the valence ionization continuum. We demonstrate that this problematic behavior can be avoided by extending the core-valence separation (CVS) scheme, which decouples the valence-occupied and core-occupied excitation manifolds, into the response domain. The accuracy of the CVS-enabled damped response theory, implemented within the EOM-EE-CCSD (EOM-CC for excitation energies with single and double excitations) framework, is assessed by comparison against damped EOM-EE-CCSD response calculations. The capabilities of the new approach are illustrated by calculations of RIXS cross sections for benzene and benzene radical cation.