A Core-Valence Separated Similarity Transformed EOM-CCSD Method for Core-excitation Spectra

Abstract: We present the theory and implementation of a core-valence separated similarity transformed EOM-CCSD (STEOM-CCSD) method for K-edge core excitation spectra. The method can select an appropriate active space using CIS natural orbitals and near black box to use. The second similarity transformation Hamiltonian is diagonalized in the space of single excitation. Therefore, the final diagonalization step is free from the convergence problem arising because of the coupling of the core-excited states with the continuum of doubly excited states. Convergence trouble can appear for the preceding core-ionized states calculation in STEOM-CCSD. A core-valence separation scheme (CVS) compatible with the natural orbital based active space selection has been implemented to overcome the problem. The CVS-STEOM-CCSD has similar accuracy as that of the standard CVS-EOM-CCSD method but comes with a lower computational cost. The modification required for the CVS scheme because of the use of CIS natural orbital is highlighted. The suitability of CVS-STEOM-CCSD for chemical application is demonstrated by simulating the K-edge spectra of glycine and thymine.