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Modeling L-edge spectra at X-ray wavelengths requires consideration of spin–orbit splitting of the 2p orbitals. We introduce a low-cost tool to compute core-level spectra that combines a spin–orbit mean-field description of the Breit–Pauli Hamiltonian with nonrelativistic excited states computed using the semi-empirical density-functional theory configuration-interaction singles (DFT/CIS) method, within the state-interaction approach. Our version of DFT/CIS was introduced recently for K-edge spectra and includes a semi-empirical correction to the core orbital energies, significantly reducing ad hoc shifts that are typically required when time-dependent (TD-)DFT is applied to core-level excitations. In combination with the core/valence separation approximation and spin–orbit couplings, the DFT/CIS method affords semiquantitative L-edge spectra at CIS cost. Spin–orbit coupling has a qualitative effect on the spectra, as demonstrated for a variety of 3d transition metal systems and main-group compounds. The use of different active orbital spaces helps to facilitate spectral assignments. We find that spin–orbit splitting has a negligible effect on M-edge spectra for 3d transition metal species.more » « lessFree, publicly-accessible full text available July 11, 2026
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Gray, Montgomery; Mandal, Aniket; Herbert, John M (, The Journal of Physical Chemistry A)Free, publicly-accessible full text available May 1, 2026
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Mandal, Aniket; Herbert, John M (, The Journal of Physical Chemistry Letters)Free, publicly-accessible full text available March 13, 2026
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Herbert, John M; Mandal, Aniket (, Journal of Chemical Theory and Computation)
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Mandal, Aniket; Berquist, Eric J; Herbert, John M (, The Journal of Chemical Physics)
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