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Assessing challenging intra‐ and inter‐molecular charge‐transfer excitations energies with double‐hybrid density functionals
Author(s) -
Brémond Éric,
Ottochian Alistar,
PérezJiménez Ángel José,
Ciofini Ilaria,
Scalmani Giovanni,
Frisch Michael J.,
SanchoGarcía Juan Carlos,
Adamo Carlo
Publication year - 2021
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26517
Subject(s) - excitation , hybrid functional , range (aeronautics) , charge (physics) , density functional theory , transfer (computing) , yield (engineering) , physics , statistical physics , molecular physics , materials science , atomic physics , chemistry , computer science , thermodynamics , quantum mechanics , parallel computing , composite material
We investigate the performance of a set of recently introduced range‐separated double‐hybrid functionals, namely ω B2‐PLYP, ω B2GP‐PLYP, RSX‐0DH, and RSX‐QIDH models for hard‐to‐calculate excitation energies. We compare with the parent (B2‐PLYP, B2GP‐PLYP, PBE0‐DH, and PBE‐QIDH) and other (DSD‐PBEP86) double‐hybrid models as well as with some of the most widely employed hybrid functionals (B3LYP, PBE0, M06‐2X, and ω B97X). For this purpose, we select a number of medium‐sized intra‐ and inter‐molecular charge‐transfer excitations, which are known to be challenging to calculate using time‐dependent density‐functional theory (TD‐DFT) and for which accurate reference values are available. We assess whether the high accuracy shown by the newest double‐hybrid models is also confirmed for those cases too. We find that asymptotically corrected double‐hybrid models yield a superior performance, especially for the inter‐molecular charge‐transfer excitation energies, as compared to standard double‐hybrid models. Overall, the PBE‐QIDH and its corresponding range‐separated RSX‐QIDH functional are recommended for general‐purpose TD‐DFT applications, depending on whether long‐range effects are expected to play a significant role.