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A newly parameterized combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian, termed core-valence separation (CVS)-QE12, is defined for the computation of K-shell core-excitation and core-ionization energies. This CVS counterpart to the recently reported QE8 Hamiltonian [Costain et al., J. Chem. Phys, 160, 224106 (2024)] is parameterized by fitting to benchmark quality ab initio data. The definition of the CVS-QE12 and QE8 Hamiltonians differ from previous CVS-DFT/MRCI parameterizations in three primary ways: (i) the replacement of the BHLYP exchange–correlation functional with QTP17 to yield a balanced description of both core and valence excitation energies, (ii) the adoption of a new, three-parameter damping function, and (iii) the introduction of separate scaling of the core-valence and valence-valence Coulombic interactions. Crucially, the parameters of the CVS-QE12 Hamiltonian are obtained via fitting exclusively to highly accurate ab initio vertical core-excitation and ionization energies computed at the CVS-EOM-CCSDT level of theory. The CVS-QE12 Hamiltonian is validated against further benchmark computations and is found to furnish K-edge core vertical excitation and ionization energies exhibiting absolute errors ≤0.5 eV at low computational cost. [ABSTRACT FROM AUTHOR]

A new combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian parameterized solely using the benchmark ab initio vertical excitation energies obtained from the QUEST databases is presented. This new formulation differs from all previous versions of the method in that the choice of the underlying exchange–correlation (XC) functional employed to construct the one-particle (orbital) basis is considered, and a new XC functional, QTP17, is chosen for its ability to generate a balanced description of core and valence vertical excitation energies. The ability of the new DFT/MRCI Hamiltonian, termed QE8, to furnish accurate excitation energies is confirmed using benchmark quantum chemistry computations, and a mean absolute error of 0.16 eV is determined for the wide range of electronic excitations included in the validation dataset. In particular, the QE8 Hamiltonian dramatically improves the performance of DFT/MRCI for doubly excited states. The performance of fast approximate DFT/MRCI methods, p-DFT/MRCI and DFT/MRCI(2), is also evaluated using the QE8 Hamiltonian, and they are found to yield excitation energies in quantitative agreement with the parent DFT/MRCI method, with the two methods exhibiting a mean difference of 0.01 eV with respect to DFT/MRCI over the entire benchmark set. [ABSTRACT FROM AUTHOR]

We introduce a perturbative approximation to the combined density functional theory and multireference configuration interaction (DFT/MRCI) approach. The method, termed DFT/MRCI(2), results from the application of quasi-degenerate perturbation theory (QDPT) and the Epstein–Nesbet partitioning to the DFT/MRCI Hamiltonian matrix. The application of QDPT obviates the need to diagonalize the large DFT/MRCI Hamiltonian; electronic energies are instead obtained as the eigenvalues of a small effective Hamiltonian, affording an orders of magnitude savings in the computational cost. Most importantly, the DFT/MRCI(2) approximation is found to be of excellent accuracy, furnishing excitation energies with a root mean squared deviation from the canonical DFT/MRCI values of less than 0.03 eV for an extensive test set of organic molecules. [ABSTRACT FROM AUTHOR]

We present a framework for the calculation of diabatic states using the combined density functional theory and multireference configuration interaction (DFT/MRCI) method. Due to restrictions present in the current formulation of the DFT/MRCI method (a lack of analytical derivative couplings and the inability to use non-canonical Kohn–Sham orbitals), most common diabatization strategies are not applicable. We demonstrate, however, that diabatic wavefunctions and potentials can be reliably calculated at the DFT/MRCI level of theory using a propagative variant of the block diagonalization diabatization method (P-BDD). The proposed procedure is validated via the calculation of diabatic potentials for LiH and the simulation of the vibronic spectrum of pyrazine. In both cases, the combination of the DFT/MRCI and P-BDD methods is found to correctly recover the non-adiabatic coupling effects of the problem. [ABSTRACT FROM AUTHOR]

We present an extension of the combined density functional theory (DFT) and multireference configuration interaction (MRCI) method (DFT/MRCI) [S. Grimme and M. Waletzke, J. Chem. Phys. 111, 5645 (1999)] for the calculation of core-excited states based on the core-valence separation (CVS) approximation. The resulting method, CVS-DFT/MRCI, is validated via the simulation of the K-edge X-ray absorption spectra of 40 organic chromophores, amino acids, and nucleobases, ranging in size from CO2 to tryptophan. Overall, the CVS-DFT/MRCI method is found to yield accurate X-ray absorption spectra (XAS), with consistent errors in peak positions of ∼2.5–3.5 eV. Additionally, we show that the CVS-DFT/MRCI method may be employed to simulate XAS from valence excited states and compare the simulated spectra to those computed using the established wave function-based approaches [ADC(2) and ADC(2)x]. In general, each of the methods yields excited state XAS spectra in qualitative and often quantitative agreement. In the instances where the methods differ, the CVS-DFT/MRCI simulations predict intensity for transitions for which the underlying electronic states are characterized by doubly excited configurations relative to the ground state configuration. Here, we aim to demonstrate that the CVS-DFT/MRCI approach occupies a specific niche among numerous other electronic structure methods in this area, offering the ability to treat initial states of arbitrary electronic character while maintaining a low computational cost and comparatively black box usage. [ABSTRACT FROM AUTHOR]