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This article compares two double-hybrid density functionals, r2SCAN-QIDH and SOS1-r2SCAN-QIDH-D4, and explains their terminology. The r2SCAN-QIDH model is a nonempirical DH model derived from adiabatic-connection formalism and second-order perturbation theory, while the SOS1-r2SCAN-QIDH-D4 model includes an empirical dispersion term. The article evaluates the performance of these models on different benchmark datasets and finds that the r2SCAN-QIDH model is accurate, while the dispersion-corrected variant is more efficient for noncovalent interactions. The article emphasizes the importance of using accurate terminology to avoid confusion between different DH approaches. The document also discusses the development of NL and D4 dispersion correction parameters for noncovalent interactions, providing tables with data from the GMTKN55 database. [Extracted from the article]

We develop and validate the SOS1-RSX-QIDH density functional, a one-parameter spin-opposite-scaled variant of the range-separated-exchange quadratic-integrand double-hybrid (RSX-QIDH) model. By entering into the family of spin-biased double hybrids, this new density functional benefits from an improved computational scaling that rivals with the one of hybrids, still conserving the accuracy of its RSX-QIDH version. As part of the latter family, this density functional is well-adapted to treat molecular systems that are particularly prone to self-interaction errors in their ground and excited states. In particular, we show that the SOS1-RSX-QIDH model is a good compromise to treat ground-state problems dealing with kinetics and has a real added value when applied to the evaluation of the excited-state properties of equilibrium and out-of-equilibrium molecular complexes. Even if spin-biased double hybrids are recognized to strongly underestimate noncovalent interactions, we notice and recommend coupling SOS1-RSX-QIDH with a nonlocal van der Waals potential, a combination that is here proved to compete with the best density-functional approximations currently in use. [ABSTRACT FROM AUTHOR]

The optical and mechanical properties of 2D semiconductors make them excellent candidates for the active components of plastic optoelectronic devices. Here, the integration of single‐layer WSe2 (1L‐WSe2) into a polystyrene (PS) film containing dispersed perylene orange (PDI‐O) molecules is investigated. The findings reveal a notable enhancement in the light emission of 1L‐WSe2, which occurs exclusively upon PDI‐O excitation and scales with the concentration of molecules in the PS film. Moreover, the increase in 1L‐WSe2 photoluminescence coincides with a quenching of the PDI‐O light emission intensity and a decrease in its lifetime. These results point to efficient long‐range interactions, such as Förster energy transfer, between PDI‐O (acting as the donor) and 1L‐WSe2 (acting as the acceptor), as the mechanism responsible for the enhanced light emission in the latter. These findings are of great interest for the development of flexible optoelectronic devices integrating active 2D materials; the polymeric matrix plays a dual role, serving as both physical support and host for organic dopants that can optimize the light emission properties of the active 2D material. [ABSTRACT FROM AUTHOR]

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In Chemistry, complexity is not necessarily associated to large systems, as illustrated by the textbook example of axial–equatorial equilibrium in mono-substituted cyclohexanes. The difficulty in modelling such a simple isomerization is related to the need for reproducing the delicate balance between two forces, with opposite effects, namely the attractive London dispersion and the repulsive steric interactions. Such balance is a stimulating challenge for density-functional approximations and it is systematically explored here by considering 20 mono-substituted cyclohexanes. In comparison to highly accurate CCSD(T) reference calculations, their axial–equatorial equilibrium is studied with a large set of 48 exchange–correlation approximations, spanning from semilocal to hybrid to more recent double hybrid functionals. This dataset, called SAV20 (as Steric A-values for 20 molecules), allows to highlight the difficulties encountered by common and more original DFT approaches, including those corrected for dispersion with empirical potentials, the 6-31G*-ACP model, and our cost-effective PBE-QIDH/DH-SVPD protocol, in modeling these challenging interactions. Interestingly, the performance of the approaches considered in this contribution on the SAV20 dataset does not correlate with that obtained with other more standard datasets, such as S66, IDISP or NC15, thus indicating that SAV20 covers physicochemical features not already considered in previous noncovalent interaction benchmarks. [ABSTRACT FROM AUTHOR]

In this Communication, we assess a panel of 18 double-hybrid density functionals for the modeling of the thermochemical and kinetic properties of an extended dataset of 449 organic chemistry reactions belonging to the BH9 database. We show that most of DHs provide a statistically robust performance to model barrier height and reaction energies in reaching the "chemical accuracy." In particular, we show that nonempirical DHs, such as PBE0-DH and PBE-QIDH, or minimally parameterized alternatives, such as ωB2PLYP and B2K-PLYP, succeed to accurately model both properties in a balanced fashion. We demonstrate, however, that parameterized approaches, such as ωB97X-2 or DSD-like DHs, are more biased to only one of both properties. [ABSTRACT FROM AUTHOR]

We recently derived a new and simple route to the determination of the range-separation parameter in range-separated exchange hybrid and double-hybrid density functionals by imposing an additional constraint to the exchange-correlation energy to recover the total energy of the hydrogen atom [Brémond et al., J. Chem. Phys. 15, 201102 (2019)]. Here, we thoroughly assess this choice by statistically comparing the derived values of the range-separation parameters to the ones obtained using the optimal tuning (OT) approach. We show that both approaches closely agree, thus, confirming the reliability of ours. We demonstrate that it provides very close performances in the computation of properties particularly prone to the one- and many-electron self-interaction errors (i.e., ionization potentials). Our approach arises as an alternative to the OT procedure, conserving the accuracy and efficiency of a standard Kohn–Sham approach to density-functional theory computation. [ABSTRACT FROM AUTHOR]

Linear and cyclic acenes are polycyclic aromatic hydrocarbons that can be viewed as building blocks of graphene nanoribbons and carbon nanotubes, respectively. While short linear acenes demonstrated remarkable efficiency in several optoelectronic applications, the longer members are unstable and difficult to synthesize as their cyclic counterparts. Recent progress in on-surface synthesis, a powerful tool to prepare highly reactive species, opens promising perspectives and motivates the computational investigations of these potentially functional molecules. Owing to their di- and poly-radical character, low-lying excited states dominated by doubly excited configurations are expected to become more important for longer members of both linear and cyclic molecules. In this work, we investigate the lowest-lying L a and the doubly excited (DE) state of linear acenes and cyclacenes, with different computational approaches, to assess the influence of the di-/poly-radical characters (increasing with the molecular dimensions) on their relative order. We show that DFT/MRCI calculations correctly reproduce the crossing of the two states for longer linear acenes, while TDUDFT calculations fail to predict the correct excitation energy trend of the DE state. The study suggests a similarity in the excited electronic state pattern of long linear and cyclic acenes leading ultimately to a lowest lying dark DE state for both. [ABSTRACT FROM AUTHOR]

In this communication, we present a new and simple route to derive range-separated exchange (RSX) hybrid and double hybrid density functionals in a nonempirical fashion. In line with our previous developments [Brémond et al., J. Chem. Theory Comput. 14, 4052 (2018)], we show that by imposing an additional physical constraint to the exchange-correlation energy, i.e., by enforcing to reproduce the total energy of the hydrogen atom, we are able to generalize the nonempirical determination of the range-separation parameter to a family of RSX hybrid density functionals. The success of the resulting models is illustrated by an accurate modeling of several molecular systems and properties, like ionization potentials, particularly prone to the one- and many-electron self-interaction errors. [ABSTRACT FROM AUTHOR]

The recent synthesis of a C18 monocyclic ring constitutes a major breakthrough as a new all-carbon disclosed form. However, modern density functional theory approaches do not lead to the correct experimental polyynic structure and favor the cumulenic one instead. We demonstrate here that this serious drawback can be solved by recently developed range-separated nonempirical schemes, independently of which kind of functional is being applied (i.e., semilocal, hybrid, or double-hybrid). [ABSTRACT FROM AUTHOR]