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Published September 12, 2017 | Supplemental Material
Journal Article Open

Linear-response time-dependent embedded mean-field theory

Abstract

We present a time-dependent (TD) linear-response description of excited electronic states within the framework of embedded mean-field theory (EMFT). TD-EMFT allows for subsystems to be described at different mean-field levels of theory, enabling straightforward treatment of excited states and transition properties. We provide benchmark demonstrations of TD-EMFT for both local and nonlocal excitations in organic molecules, as well as applications to chlorophyll a, solvatochromic shifts of a dye in solution, and sulfur K-edge X-ray absorption spectroscopy (XAS). It is found that mixed-basis implementations of TD-EMFT lead to substantial errors in terms of transition properties; however, as previously found for ground-state EMFT, these errors are largely eliminated with the use of Fock-matrix corrections. These results indicate that TD-EMFT is a promising method for the efficient, multilevel description of excited-state electronic structure and dynamics in complex systems.

Additional Information

© 2017 American Chemical Society. Received: June 27, 2017; Published: August 7, 2017. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. T.F.M. and F.D. additionally acknowledge support from the Air Force Office of Scientific Research under Award Number FA9550-17-1-0102, and T.F.M. acknowledges support from a Camille Dreyfus Teacher-Scholar Award. F.R.M. and T.T. acknowledge support from the Engineering and Physical Sciences Research Council (EP/M013111/1).

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August 19, 2023
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