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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]

Due to the largely recognized utility of bioluminescence in many fields, a wide variety of luciferase–luciferin systems have been investigated in order to find the best-suited for a number of different applications. The collected knowledge has allowed the identification of a few necessary, or at least desirable, properties, such as bright luminescence, low background signal and small dimension of the enzyme that must exhibit structural stability at operating conditions. The NanoLuc-furimazine pair seems to meet all these requirements, but the mechanism of the reaction and the characteristics of the species responsible for the emission remain unknown. The aim of this study is to identify the luminescent product among the possible forms of oxidized furimazine and to understand how the chemical form and structure of the system, before and after the oxidation, are involved into the reaction mechanism and determine emission. To do this, we consider two possible forms of furimazine, the keto and the enol one, and test which of them is the most plausible candidate in the bioluminescence process on the basis of enzyme–substrate interactions from docking calculations. A similar procedure is repeated for three possible forms of the furimamide luminescent product, and their properties in the protein environment are then evaluated via QM/MM calculations. In contrast with previous indications, our simulations well support the involvement of the enol form of furimazine as reagent and point to the zwitterionic forms of furimamide as emissive species. [ABSTRACT FROM AUTHOR]

Setting up computational approaches enabling the correct prediction of the photophysical properties of rhodamine B (RB) derivatives and their aggregates (referred to as dimers here) is of fundamental importance to rationally drive the design of novel systems of applicative relevance, such as artificial light-harvesting nanosystems. Currently, approaches rooted in time-dependent density functional theory (TD-DFT), which are appealing for their relatively low computational cost, nonetheless have limitations in terms of accuracy, especially while considering RB dimeric species. In this work, we investigated the performances of optimally tuned range-separated hybrid functionals for describing the excited states of RB and its H dimer, focusing on dimeric charge-transfer (CT) states. We compared different optimal tuning (OT) procedures including or not solvent screening. The results show that the properties of CT states, such as their CT extent, brightness and relative energy ordering, are crucially affected by the Hartree–Fock exchange amount dictated by OT, which is in turn driven by the chosen asymptotic behavior. Finally, to understand the dissimilar pictures provided for the CT states by different tuning approaches, we performed an extensive analysis aimed at elucidating how CT states are affected by range-separation parameters. As a result, a simple procedure is finally provided for easily achieving a unique functional to be applied on both monomer and dimers, its current limitations are highlighted and possible perspectives for future development are envisaged. [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]

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]

Transition Metal Complexes (TMCs) are known for the rich variety of their excited states showing different nature and degrees of locality. Describing the energies of these excited states with the same degree of accuracy is still problematic when using time-dependent density functional theory in conjunction with the most current density functional approximations. In particular, the presence of unphysically low lying excited states possessing a relevant Charge Transfer (CT) character may significantly affect the spectra computed at such a level of theory and, more relevantly, the interpretation of their photophysical behavior. In this work, we propose an improved version of the MAC index, recently proposed by the authors and collaborators, as a simple and computationally inexpensive diagnostic tool that can be used for the detection and correction of the unphysically predicted low lying excited states. The analysis, performed on five prototype TMCs, shows that spurious and ghost states can appear in a wide spectral range and that it is difficult to detect them only on the basis of their CT extent. Indeed, both delocalization of the excited state and CT extent are criteria that must be combined, as in the MAC index, to detect unphysical states. [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]

Organic luminophores displaying one or more forms of luminescence enhancement in solid state are extremely promising for the development and performance optimization of functional materials essential to many modern key technologies. Yet, the effort to harness their huge potential is riddled with hurdles that ultimately come down to a limited understanding of the interactions that result in the diverse molecular environments responsible for the macroscopic response. In this context, the benefits of a theoretical framework able to provide mechanistic explanations to observations, supported by quantitative predictions of the phenomenon, are rather apparent. In this perspective, we review some of the established facts and recent developments about the current theoretical understanding of solid-state luminescence enhancement (SLE) with an accent on aggregation-induced emission (AIE). A description of the macroscopic phenomenon and the questions it raises is accompanied by a discussion of the approaches and quantum chemistry methods that are more apt to model these molecular systems with the inclusion of an accurate yet efficient simulation of the local environment. A sketch of a general framework, building from the current available knowledge, is then attempted via the analysis of a few varied SLE/AIE molecular systems from literature. A number of fundamental elements are identified offering the basis for outlining design rules for molecular architectures exhibiting SLE that involve specific structural features with the double role of modulating the optical response of the luminophores and defining the environment they experience in solid state. [ABSTRACT FROM AUTHOR]