Environmental Effects with Frozen-Density Embedding in Real-Time Time-Dependent Density Functional Theory Using Localized Basis Functions

Abstract

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Local approaches for electric dipole moments in periodic systems and their application to real-time time-dependent density functional theory

“…However, recent advances have shown that there is interest in accelerating RT-TDDFT calculations and Ehrenfest molecular dynamics (EMD) via DFT embedding approaches. [48][49][50][51][52][53][54]…”

Environment effects on X-ray absorption spectra with quantum embedded real-time Time-dependent density functional theory approaches

“…The Frozen Density (FDE) 25,33,34,73 and Block-Orthogonalized Manby-Miller embedding (BOMME) approaches 62 , and their extension to the rt-TDDFT framework has been described in previous works 50,65 . In this Section, after brief recapitulation of the rt-TDDFT method, we will outline analogies and differences of rt-FDE and rt-BOMME approaches.…”

“…The code implementing the rt-FDE in the Psi4Numpy framework used in this work is part of the PyBertha package 50,90,91 (revision 3c752072). The code implementing the (rt-)BOMME approach is under version control (Git) but does not yet have a public release version (one is envisaged for 2022).…”

“…It should be noted that such couplings between the response of subsystems to external perturbation can also be taken into account in a frequency-domain formulation, but at the expense of determining second (or higher) order derivatives of the interaction energy [41][42][43][44][45][46] . That said, applications of linear-response or real-time TDDFT-in-DFT showed that in many cases, the coupling between the response of different subsystems can be ignored and a socalled "uncoupled" TDDFT-in-DFT approach can yield accurate results [47][48][49][50] , provided the coupling between subsystems in the ground state is well described by the embedding potential representing the subsystems' interaction. FDE-based calculation has been shown to perform well for situations in which there are no strong interactions between subsystems, such as covalent bonds.…”

ΔSCF with Subsystem Density Embedding for Efficient Nonadiabatic Molecular Dynamics in Condensed-Phase Systems

“…40 Density embedding schemes were generalized to excited electronic states by linear-response as well as real-time TD-DFT [41][42][43][44][45][46] and applied for calculations of a number of spectroscopic properties, including for some impressively large systems with multiple chromophores. [47][48][49][50][51][52] But unlike these static calculations, to the best of our knowledge, there is only one report of using density embedding methods for simulating NA processes in a dynamic manner using Ehrenfest NA molecular dynamics (MD) with real-time TD-DFT. 29 In this work, we combine the power of the subsystem DFT with the practicality of the ∆SCF method to obtain excited electronic states.…”