Theoretical Calculation of Core-Excited States along Dissociative Pathways beyond Second-Order Perturbation Theory.

We extend the multireference driven similarity renormalization (MR-DSRG) method to compute core-excited states by combining it with a GASSCF treatment of orbital relaxation and static electron correlation effects. We consider MR-DSRG treatments of dynamical correlation truncated at the level of perturbation theory (DSRG-MRPT2/3) and iterative linearized approximations with one- and two-body operators [MR-LDSRG(2)] in combination with a spin-free exact-two-component (X2C) one-electron treatment of scalar relativistic effects. This approach is calibrated and tested on a series of 16 core-excited states of five closed- and open-shell diatomic molecules containing first-row elements (C, N, and O). All GASSCF-MR-DSRG theories show excellent agreement with experimental adiabatic transitions energies, with mean absolute errors ranging between 0.17 and 0.35 eV, even for the challenging partially doubly excited states of the N molecule. The vibrational structure of all these transitions, obtained from using a full potential energy scan, shows a mean absolute error as low as 25 meV for DSRG-MRPT2 and 12/13 meV for DSRG-MRPT3 and MR-LDSRG(2). We generally find that a treatment of dynamical correlation that goes beyond the second-order level in perturbation theory improves the accuracy of the potential energy surface, especially in the bond-dissociation region.