Optimal Tuning Perspective of Range-Separated Double Hybrid Functionals

Prokopiou, Georgia; Hartstein, Michal; Govind, Niranjan; Kronik, Leeor

doi:10.1021/acs.jctc.2c00082

Cited by 8 publications

(4 citation statements)

References 131 publications

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“…This is not surprising because the energies of virtual orbitals both in Hartree-Fock and DFT are calculated with less reliability. To some extent, it may be remedied through the use of optimally tuned range-separated functionals [30,31]. The intercept on the linear regressions of E ox (E red ) vs. HOMO(LUMO) or vs. IP(EA) incorporates all the systematic errors and the absolute potential of the reference electrode.…”

Section: Ground State Structures and Molecular Orbitalsmentioning

confidence: 99%

Theoretical Study of Structure and Photophysics of Homologous Series of Bis(arylydene)cycloalkanones

Starostin¹,

Freidzon²,

Gromov³

2023

Preprint

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Photophysical properties of a series of bis(arylydene)cycloalkanone dyes with various donor substituentns are studied by quantum chemistry. Their capacity for luminescence and nonradiative relaxation through trans-cis isomerization is related to their structure, in particular, to the donor capacity of the substituents and the degree of conjugation due to the central cycloalkanone moiety. It is shown that cyclohexanone central moiety introduces distortions and disrupts the conjugation, thus leading to a nonmonotonic change in their properties. The increasing donor capacity of the substituents causes increase in the HOMO energy (raise of the oxidation potential) and decrease in the HOMO-LUMO gap, which results in the red shift of the absorption spectra. The ability of the excited dye to relax through fluorescence or through trans-cis isomerization is governed by the height of the barrier between the Franck–Condon and S1-S0 conical intersection regions on the potential energy surface of the lowest π-π* excited state. This barrier also correlates with the donor capacity of the substituents and the degree of conjugation between the central and donor moieties. The calculated fluorescence and trans-cis isomerization rates are in good agreement with the observed fluorescence quantum yields.

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Section: Ground State Structures and Molecular Orbitalsmentioning

confidence: 99%

Theoretical Study of Structure and Photophysics of Homologous Series of Bis(arylydene)cycloalkanones

Starostin¹,

Freidzon²,

Gromov³

2023

Preprint

View full text Add to dashboard Cite

show abstract

“…The eigenvalue of the lowest unoccupied molecular orbital (LUMO) also shows important deviations from the negative of the vertical electron affinity (VEA), −A, due to the deviation from the linearity condition [8,9]. These undesirable behaviors have been identified as fractional charge errors which translate into either delocalization (convex deviations) or localization (concave deviations) errors [9][10][11]. It has been found that DFAs based on the local density approximation, generalized gradient approximation (GGA), or meta-GGA show a rather large convex curve for the energy as a function of N, while Hartree-Fock (HF) yields a concave deviation (a fact that has been exploited in the development of several DFAs including optimally-tuned range-separated hybrids (OTRSH) [12][13][14][15][16][17][18][19][20][21]).…”

Section: Introductionmentioning

confidence: 99%

Exploiting a derivative discontinuity estimate for accurate G0W0 ionization potentials and electron affinities

Mejia-Rodriguez

2024

Electron. Struct.

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The GW approximation has become an important tool for predicting charged excitations of isolated molecules and condensed systems. Its popularity can be attributed to many factors, including a favorable scaling and relatively good accuracy. In practical applications, the GW is often performed as a one-shot perturbation known as G 0 W 0. Unfortunately, G 0 W 0 suffers from a strong starting point dependence and is often not as accurate as one would need. Self-consistent GW methodologies alleviate these problems but come with a marked increase in computational cost. In this manuscript, we propose the use of an estimate of the exchange-correlation derivative discontinuity to provide a remarkably good starting point for G 0 W 0 calculations, yielding ionization potentials and electron affinities with eigenvalue self-consistent GW quality at no additional cost. We assess the quality of the resulting methodology with the GW100 benchmark set and compare its advantages over other similar methods.

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“…Following the idea of the RSH+MP2 22 method, Kalai and Toulouse 40 proposed a general scheme for RSDHs, where they recommended using range-separation for both exchange and PT2 correlation terms. Recently, Prokopiou et al 41 have developed an optimally tuned RSDH functional by substituting the degeneracy-corrected perturbation theory (DCPT2 42 ) for GLPT2. (We note in passing that the analytical first 43 and second 44 derivatives for DHs are available in the literature, not just in the gas phase but also in continuum solvents.…”

Section: Introductionmentioning

confidence: 99%

Benefits of Range-Separated Hybrid and Double-Hybrid Functionals for a Large and Diverse Data Set of Reaction Energies and Barrier Heights

2022

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To better understand the thermochemical kinetics and mechanism of a specific chemical reaction, an accurate estimation of barrier heights (forward and reverse) and reaction energies is vital. Because of the large size of reactants and transition state structures involved in real-life mechanistic studies (e.g., enzymatically catalyzed reactions), density functional theory remains the workhorse for such calculations. In this paper, we have assessed the performance of 91 density functionals for modeling the reaction energies and barrier heights on a large and chemically diverse data set (BH9) composed of 449 organic chemistry reactions. We have shown that range-separated hybrid functionals perform better than the global hybrids for BH9 barrier heights and reaction energies. Except for the PBE-based range-separated nonempirical double hybrids, range separation of the exchange term helps improve the performance for barrier heights and reaction energies. The 16-parameter Berkeley double hybrid, ωB97M(2), performs remarkably well for both properties. However, our minimally empirical range-separated double hybrid functionals offer marginally better accuracy than ωB97M(2) for BH9 barrier heights and reaction energies.

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Optimal Tuning Perspective of Range-Separated Double Hybrid Functionals

Cited by 8 publications

References 131 publications

Theoretical Study of Structure and Photophysics of Homologous Series of Bis(arylydene)cycloalkanones

Theoretical Study of Structure and Photophysics of Homologous Series of Bis(arylydene)cycloalkanones

Exploiting a derivative discontinuity estimate for accurate G0W0 ionization potentials and electron affinities

Benefits of Range-Separated Hybrid and Double-Hybrid Functionals for a Large and Diverse Data Set of Reaction Energies and Barrier Heights

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