Electron dynamics method using a locally projected group diabatic Fock matrix for molecules and aggregates

TL;DR

This paper introduces a novel electron dynamics method combining real-time density functional theory with a projected group diabatic Fock matrix, enabling efficient analysis of complex molecular excited states with reduced computational cost.

Contribution

The method reduces Hilbert space size using a projection technique, maintaining accuracy while enabling efficient simulation of electron dynamics in molecules and aggregates.

Findings

Half of the orbitals can be reduced without losing accuracy.

The method successfully describes electron dynamics in a donor-acceptor dimer.

It provides a computationally feasible approach for complex molecular systems.

Abstract

We propose a method using reduced size of Hilbert space to describe an electron dynamics in molecule and aggregate based on our previous theoretical scheme [ T. Yonehara and T. Nakajima, J. Chem. Phys. \textbf{147}, 074110 (2017) ]. The real-time time-dependent density functional theory is combined with newly introduced projected group diabatic Fock matrix. First, this projection method is applied to a test donor--acceptor dimer, namely, a naphthalene--tetracyanoethylene with and without initial local excitations and light fields. Secondly, we calculate an absorption spectrum of five-unit-polythiophene monomer. The importance of feedback of instantaneous density to Fock matrix is also clarified. In all cases, half of the orbitals were safely reduced without loss of accuracy in descriptions of properties. The present scheme provides one possible way to investigate and analyze a complex excited electron dynamics in molecular aggregates within a moderate computational cost.