Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 17, Issue 5, Pages 3031-3038Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.1c00144
Keywords
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division [KC-030105172685, DE-AC0276SF00515, DE-SC0019277]
- NSF GRFP [DGE1762114]
- Office of Biological and Environmental Research
- DOE [DE-AC05-76RL1830]
- National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science [DE-AC0205CH11231]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-76SF00515]
- U.S. Department of Energy (DOE) [DE-SC0019277] Funding Source: U.S. Department of Energy (DOE)
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The method utilizes TDDFT theory to calculate the light-matter couplings between different excited state manifolds in 4d transition metal systems, for solving RIXS and other two-photon spectroscopy problems. By avoiding the need to solve expensive TDDFT quadratic-response equations, the method can capture experimental features and enable the assignment of experimental peaks.
We present a time-dependent density functional theory (TDDFT) approach to compute the light-matter couplings between two different manifolds of excited states relative to a common ground state in the context of 4d transition metal systems. These quantities are the necessary ingredients to solve the Kramers-Heisenberg (KH) equation for resonant inelastic X-ray scattering (RIXS) and several other types of two-photon spectroscopies. The procedure is based on the pseudo-wavefunction approach, where the solutions of a TDDFT calculation can be used to construct excited-state wavefunctions, and on the restricted energy window approach, where a manifold of excited states can be rigorously defined based on the energies of the occupied molecular orbitals involved in the excitation process. Thus, the present approach bypasses the need to solve the costly TDDFT quadratic-response equations. We illustrate the applicability of the method to 4d transition metal molecular complexes by calculating the 2p4d RIXS maps of three representative ruthenium complexes and comparing them to experimental results. The method can capture all the experimental features in all three complexes to allow the assignment of the experimental peaks, with relative energies correct to within similar to 0.6 eV at the cost of two independent TDDFT calculations.
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