Application of recent double-hybrid density functionals to low-lying singlet-singlet excitation energies of large organic compounds

Abstract

The present work assesses some recently developed double-hybrid density functionals (B2π -PLYP, PBE0-DH, and PBE0-2) using linear-response Tamm-Dancoff Time-Dependent Density Functional Theory. This assessment is achieved against experimentally derived low-lying excitation energies of large organic dyes of recent interest, including some excitations dominated by charge-transfer transitions. Comparisons are made with some of the best-performing methods established from the literature, such as PBE0 or B3LYP hybrid or the recently proposed B2-PLYP and B2GP-PLYP doublehybrid models, to ascertain their quality and robustness on equal footing. The accuracy of parameterfree or empirical forms of double-hybrid functionals is also briefly discussed. Generally speaking, it turns out that double-hybrid expressions always provide more accurate estimates than corresponding hybrid methods. Double-hybrid functionals actually reach averaged accuracies of 0.2 eV, that can be admittedly considered close to any intended accuracy limit within the present theoretical framework.

Double‐hybrid density functionals

“…(17), one obtains the Tamm-Dancoff approximation (TDA), 173,174 which has been tested in 2007 for B2-PLYP and very recently also for the PBE0-DH and PBE0-2 functionals. 175 TD-DHDFT calculations can be carried out with any program that has TD-DFT and CIS(D) algorithms implemented. Practically, however, TD-DHDFs have only been tested with a group-own program in the Grimme group and they are currently available for the scientific community in the TDA form in the free program ORCA.…”

“…Results are depicted for BLYP and PBE based functionals, including GGA (BLYP and PBE), hybrid (B3-LYP and PBE0), and double-hybrids (B2-PLYP, B2GP-PLYP, PBE0-DH, and PBE0-2) results. 69,175 The PBE0-DH and PBE0-2 numbers are based on TDA-DFT calculations and taken from Ref 175, while PBE and PBE0 results were recalculated herein based on full TD-DFT (see Supporting Information). All other results are taken from Ref 69.…”

New Developments of a Multifrequency Virtual Spectrometer: Stereo‐Electronic, Dynamical, and Environmental Effects on Chiroptical Spectra

“…In this connection the development of methods rooted in Density Functional Theory (DFT) and its time-dependent (TD-DFT) extension have revolutionized the field, giving access to reliable computations of medium-to large-size flexible systems. 5 Although some limitations are still present and development of improved functionals is a very active research field, [6][7][8] we already have at our disposal robust and reliable approaches at least for ground and valence excited states not involving too large multi-reference and/or charge transfer contributions (see Ref. 9 and references therein for examples of applications).…”

Describing excited states of [n]cycloparaphenylenes by hybrid and double-hybrid density functionals: from isolated to weakly interacting molecules

“…This scheme has been shown to behave accurately for a representative set of organic molecules [58][59][60].…”