Optoelectronic and Excitonic Properties of Oligoacenes: Substantial Improvements from Range-Separated Time-Dependent Density Functional Theory

TL;DR

This study demonstrates that range-separated time-dependent density functional theory significantly improves the accuracy of optoelectronic and excitonic property predictions in linear acenes, outperforming conventional hybrid functionals.

Contribution

The paper shows that a full 100% Hartree-Fock range separation within TDDFT is essential for accurately describing low-lying excitations and excitonic properties in acenes, addressing limitations of traditional methods.

Findings

Range-separated TDDFT eliminates errors in La and Lb state energies.

Conventional hybrid functionals overdelocalize excitons and underestimate energy gaps.

Full Hartree-Fock range separation is necessary for accurate excitonic descriptions.

Abstract

The optoelectronic and excitonic properties in a series of linear acenes (naphthalene up to heptacene) are investigated using range-separated methods within time-dependent density functional theory (TDDFT). In these rather simple systems, it is well-known that TDDFT methods using conventional hybrid functionals surprisingly fail in describing the low-lying La and Lb valence states, resulting in large, growing errors for the La state and an incorrect energetic ordering as a function of molecular size. In this work, we demonstrate that the range-separated formalism largely eliminates both of these errors and also provides a consistent description of excitonic properties in these systems. We further demonstrate that re-optimizing the percentage of Hartree-Fock exchange in conventional hybrids to match wavefunction-based benchmark calculations still yields serious errors, and a full 100% Hartree-Fock range separation is essential for simultaneously describing both of the La and Lb transitions. Based on an analysis of electron-hole transition density matrices, we finally show that conventional hybrid functionals overdelocalize excitons and underestimate quasiparticle energy gaps in the acene systems. The results of our present study emphasize the importance of both a range-separated and asymptotically-correct contribution of exchange in TDDFT for investigating optoelectronic and excitonic properties, even for these simple valence excitations.