An efficient and accurate approximation to time-dependent density functional theory for systems of weakly coupled monomers

Abstract

A novel formulation of time-dependent density functional theory (TDDFT) is derived, based on non-orthogonal, absolutely-localized molecular orbitals (ALMOs). We call this approach TDDFT(MI), in reference to ALMO-based methods for describing molecular interactions (MI) that have been developed for ground-state applications. TDDFT(MI) is intended for efficient excited-state calculations in systems composed of multiple, weakly interacting chromophores. The efficiency is based upon (1) a local excitation approximation; (2) monomer-based, singly-excited basis states; (3) an efficient localization procedure; and (4) a one-step Davidson method to solve the TDDFT(MI) working equation. We apply this methodology to study molecular dimers, water clusters, solvated chromophores, and aggregates of naphthalene diimide that form the building blocks of self-assembling organic nanotubes. Absolute errors of 0.1-0.3 eV with respect to supersystem methods are achievable for these systems, especially for cases involving an excited chromophore that is weakly coupled to several explicit solvent molecules. Excited-state calculations in an aggregate of nine naphthalene diimide monomers are ∼40 times faster than traditional TDDFT calculations.

Crystal structure, chemical reactivity, kinetic and thermodynamic studies of new ligand derived from 4-hydroxycoumarin: Interaction with SARS-CoV-2

“…The TD-DFT method [ 40 , 41 ] is a reliable approach widely used to predict the spectra of electronic absorptions. The theoretical prediction of the electron absorption spectrum of L TA was realized using the TD-DFT/B3LYP/6–31+ G (d) method on optimized geometries.…”

Quantum Mechanics / Extremely Localized Molecular Orbital Embedding Strategy for Excited-States. 1. Coupling to Time-Dependent Density Functional Theory

“…Nevertheless, although quite favorable, this computational scaling does not allow a straightforward use of basic TDDFT to investigate extended systems and, for this reason, different strategies have been devised in order to further reduce the computational cost of the method. For instance, it is worth mentioning the linearscaling approaches based on the localized nature of atomic [13][14][15] or molecular orbitals [16][17][18][19][20] , or those based on fragmentation techniques, such as the fragment molecular orbital (FMO) method 21 . In this framework, it is also very important to consider the efforts to combine Time-Dependent Density Functional Theory with different embedding strategies.…”

GPU‐Accelerated Large‐Scale Excited‐State Simulation Based on Divide‐and‐Conquer Time‐Dependent Density‐Functional Tight‐Binding

“…Therefore, theoretical developments to reduce such communication are essential to achieve high performance of GPU implementations. Linear‐scaling fragmentation methods, which divide an entire system into several fragments, could reduce the slow memory access and avoid the shortfalls of GPU memory by separately solving the problems in individual fragments …”