Calibration of several first excited state properties for organic molecules through systematic comparison of TDDFT with experimental spectra

Abstract

Time-dependent density functional theory (TDDFT) is a powerful computational tool for investigating excitation properties in organic electronics, and it holds significant potential for high-throughput virtual screening (HTVS) in this field. While most benchmarks focus on excitation energies, less attention has been paid to evaluating the accuracy of computed oscillator strengths and exciton reorganization energies against experimental data. In this work, we provide a systematic approach to evaluate in parallel the accuracy of these three quantities on the basis of a suitable fitting of the experimental absorption spectra of 71 molecules in solution. After considering 18 computational methodologies, the results from the M06-2X/def2-TZVP/PCM method demonstrate the strongest correlation with experimental data across the desired properties. For HTVS, the M06-2X/6-31G(d)/PCM method appears to be a particularly convenient choice among all methodologies due to its balance of computational efficiency and accuracy. Our results provide an additional benchmark needed before employing TDDFT methods for the discovery and design of organic electronic molecules.