Evaluation of Local Hybrid Functionals for Electric Properties: Dipole Moments and Static and Dynamic Polarizabilities

Abstract

Local hybrid functionals are a class of exchange-correlation functionals that feature a real-space dependent admixture of exact (Hartree− Fock like) exchange governed by a local mixing function. Recently we reported the LH20t functional with wide chemical applicability and excellent performance for the GMTKN55 main-group energetics test suite (M. Haasler et al., J. Chem. Theory Comput. 2020, 16, 5645−5657). Here, we present a systematic evaluation of earlier and recent local hybrid functionals for large test sets of dipole moments and static polarizabilities and for a smaller set of dynamic polarizabilities for heterocycles. Comparisons with coupled-cluster benchmark data show robust performance of all investigated local hybrids for dipole moments and polarizabilities. The two best local hybrids are the new LH20t and LH14t-calPBE. LH20t gives a percentage-relative mean-square deviation of 5.87% for the dipole moment test set and one of 4.30% for static polarizabilities. This is only slightly inferior to the currently best performances among rung 4 functionals. Most notably, no large outliers are observed in contrast to some other hybrid functionals. This shows that the current most highly parametrized (nineparameter) LH20t functional clearly produces not only good energetics but also accurate electron densities and electric-field responses. The influences of various aspects of local hybrids are examined to aid in the further development of this class of functionals.

Reliable TDDFT Protocol Based on a Local Hybrid Functional for the Prediction of Vibronic Phosphorescence Spectra Applied to Tris(2,2′-bipyridine)-Metal Complexes

“…40,43−45 For the LMF, various models were suggested, of which a scaled version of the iso-orbital indicator τ W,σ (r)/τ σ (r), referred to as t-LMF, has proven to be well suited. 40 Despite early concerns regarding the feasibility of efficient implementation, LHs are now available for a wide range of functionalities and properties including GS energies, 46 SCF, 47 and gradients, 48 LR-TDDFT energies, 49 polarizabilities, 50,51 and gradients, 52 nuclear magnetic shieldings, 53 nuclear spin−spin couplings, 54 hyperfine couplings (and electronic g-tensors), 55 as well as in extensions to two-component relativistic implementations 50,55 and as starting points for the calculation of ionization potentials with the G 0 W 0 method. 56 In an early validation study of triplet vertical excitation energies (VEEs), LHs based on a common t-LMF 57 were found to perform excellently on the Thiel test set.…”

“…The inclusion of a calibration function to correct for the gauge ambiguity of exchange-energy densities is neglected here and discussed elsewhere. ,− For the LMF, various models were suggested, of which a scaled version of the iso-orbital indicator τ W,σ ( r )/τ σ ( r ), referred to as t-LMF, has proven to be well suited . Despite early concerns regarding the feasibility of efficient implementation, LHs are now available for a wide range of functionalities and properties including GS energies, SCF, and gradients, LR-TDDFT energies, polarizabilities, , and gradients, nuclear magnetic shieldings, nuclear spin–spin couplings, hyperfine couplings (and electronic g-tensors), as well as in extensions to two-component relativistic implementations , and as starting points for the calculation of ionization potentials with the G 0 W 0 method …”

High-Throughput Predictions of Metal–Organic Framework Electronic Properties: Theoretical Challenges, Graph Neural Networks, and Data Exploration

“…Beyond band gaps, it is well-established that different DFAs can change how the charge density is distributed in a given material. [84][85][86][87][88] Furthermore, partial atomic charges (which can be computed directly from the underlying charge density) are commonly used in molecular simulations of MOFs and can be used to interpret trends when modeling redox processes and chemical reactions. 89,90 One such method to compute partial atomic charges, the sixth-generation Density Derived Electrostatic and Chemical (DDEC6) partitioning scheme, [91][92][93] has found widespread use in molecular simulations of MOFs 89 (e.g.…”

Is CCSD(T) a proper standard for dipole moment calculations? An analysis considering diverse diatomic species

“…2 In the DFT front, benchmarking studies most commonly focus on energetic properties, but recently there has been increased interest in understanding performance in non-energetic properties most notably the electric dipole moment. [3][4][5][6][7] These benchmark studies generally benchmark by comparing approximate DFT results against CCSD(T) calculations, which are viewed as the "gold standard" and assumed as accurate. However, this assumption has not been tested (and may not be accurate) for a diverse range of systems, particularly those containing transition metals or for van der Waals complexes.…”