Equation of motion coupled-cluster study of core excitation spectra II: Beyond the dipole approximation

Abstract

We present the time-independent (TI) and time-dependent (TD) equation of motion coupled-cluster (EOM-CC) oscillator strengths not limited to those obtained by the dipole approximation. For the conventional TI-EOM-CC, we implement all the terms in the multipole expansion through second order that contributes to the oscillator strength. These include contributions such as magnetic dipole, electric quadrupole, electric octupole, and magnetic quadrupole. In TD-EOM-CC, we only include the quadrupole moment contributions. This augments our previous work [Y. C. Park, A. Perera, and R. J. Bartlett, J. Chem. Phys. 151, 164117 (2019)]. The inclusion of the quadrupole contributions (and all the other contributions through second order in the case of TI-EOM-CCSD) enables us to obtain the intensities for the pre-edge transitions in the metal K-edge spectra, which are dipole inactive. The TI-EOM-CCSD and TD-EOM-CCSD spectra of Ti4+ atoms are used to showcase the implementation of the second-order oscillator strengths. The origin of 1s → e and 1s → t2 in core spectra from iron tetrachloride and titanium tetrachloride is discussed and compared with the experiment.