Systematic comparison of DFT and CCSD dipole moments, polarizabilities and hyperpolarizabilities

Karne, Anagha S.; Vaval, Nayana; Pal, Sourav; Vásquez-Pérez, José Manuel; Köster, Andreas M.; Calaminici, Patrizia

doi:10.1016/j.cplett.2015.06.046

Cited by 19 publications

(12 citation statements)

References 44 publications

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“…One should also mention that generalized gradient approximation (GGA) functional such as PBE have intrinsic failures regarding the calculation of hyperpolarizabilities. 61 However, the relative values as compared to TZP calculations are very similar, with the exception of the PBE/TZ2P calculation on the PBE structure, which is somewhat larger. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 The HOMO-LUMO (HL) gaps of the clusters and their static first hyperpolarizabilities β 0 are shown in Table 2.…”

Section: Resultsmentioning

confidence: 73%

“…One should also mention that generalized gradient approximation (GGA) functional such as PBE has intrinsic failures regarding the calculation of hyperpolarizabilities. 61 However, the relative values as compared to TZP calculations are very similar, with the exception of the PBE/TZ2P calculation on the PBE structure, which is somewhat larger.…”

Section: ■ Introductionmentioning

confidence: 80%

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Nonlinear Optical Properties of Thiolate-Protected Gold Clusters: A Theoretical Survey of the First Hyperpolarizabilities

2015

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A series of thiolate-protected gold clusters has been successfully crystallized in recent years, and on the basis of these crystal structures, we investigate the static first hyperpolarizabilities β 0 of eight model clusters [Au m (SH) n ] z (m = 18 -38) by means of density-functional theory. We used simplified ligands -SH, which may lead to higher symmetries than in actual systems (e.g. withSCH2CH2Ph or -SPh ligands). A dependence of the obtained values on the exchange-correlation functional during geometry optimization was found. No correlation between cluster size and β 0 was identified. Instead, the symmetry of the clusters seems to dominate the NLO properties. Our survey predicts strong NLO responses in the chiral Au 38 (SR) 24 cluster, whereas centrosymmetric structures such as the [Au 25 (SR) 18 )] -yield hyperpolarizabilities close to zero. This is in line with recent experimental results obtained by second-harmonic generation. The centrosymmetry of the Au 25 cluster is efficiently destroyed by ligand exchange, as demonstrated by the inclusion of chiral, bidentate ligands (1,1'-binapthyl-2,2'-dithiol, 1,1'-biphenyl-2,2'-dithiol) and two thiophenolate ligands. This induces significant hyperpolarizabilities, surpassing those of intrinsically chiral clusters (e.g. Au 38 (SH) 24 ). Our results are of significance for the use of monolayer-protected noble metal clusters as contrast agents in NLO imaging applications.

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Section: Resultsmentioning

confidence: 73%

Section: ■ Introductionmentioning

confidence: 80%

Nonlinear Optical Properties of Thiolate-Protected Gold Clusters: A Theoretical Survey of the First Hyperpolarizabilities

2015

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“…The polarizability tensor components are calculated from the perturbed density matrix elements P μν (λ) (ω) given by eq and dipole moment integral as Here λ and κ refer to components of the electric field and dipole moment, respectively. From the polarizability tensor in its principle axes system, the average polarizabilities α̅(ω) and polarizability anisotropies, |Δα(ω)| 2 , are calculated by Four-center ERI reference calculations were performed with NWChem using the default keywords.…”

Section: Computational Detailsmentioning

confidence: 99%

“…One of the successes of the range-separated hybrid functionals is for molecular polarizability calculations. Although coupled-cluster (CC) , calculations are in principle more reliable for polarizabilities, their unfavorable computational scaling with system size makes them only partially suitable for systematic polarizability studies . Thus, range-separated hybrid calculations of polarizabilities are the current state-of-the-art for systematic polarizability and hyperpolarizability studies.…”

Section: Introductionmentioning

confidence: 99%

Self-Consistent Auxiliary Density Perturbation Theory

Delesma

Delgado-Venegas

Salahub

et al. 2021

J. Chem. Theory Comput.

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The working equations for the extension of auxiliary density perturbation theory (ADPT) to hybrid functionals, employing the variational fitting of the Fock potential, are derived. The response equations in the resulting self-consistent ADPT (SC-ADPT) are solved iteratively with an adapted Eirola–Nevanlinna algorithm. As a result, a memory and CPU time efficient implementation of perturbation theory free of four-center electron repulsion integrals (ERIs) is obtained. Our validation calculations of SC-ADPT static and dynamic polarizabilities show quantitative agreement with corresponding coupled perturbed Hartree–Fock and Kohn–Sham results employing four-center ERIs. The comparison of SC-ADPT hybrid functional polarizabilities with coupled cluster reference calculations yield semiquantitative agreement. The presented systematic study of the dynamic polarizabilities of oligothiophenes shows that hybrid functionals can overcome the pathological misplacement of excitation poles by the local density and generalized gradient approximations. Good agreement with experimental dynamic polarizabilities for all studied oligothiophenes is achieved with range-separated hybrid functionals in the framework of SC-ADPT.

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“…Besides some smaller studies, − by far the most comprehensive benchmark data sets available to date for dipole moments and static polarizabilities are those by Hait and Head-Gordon. , They generated CCSD(T) reference values extrapolated to the complete basis-set limit (CBS) for 152 dipole moments (HHdip-152) and polarizabilities (HHpol-132) for 132 small molecules and atoms, and they assessed the performance of a considerable number of popular and modern XC functionals. While improvements were seen for both properties when stepping up the Jacob’s Ladder of XC functionals, differences in performance between individual functionals from the same rung were substantial.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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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.

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Systematic comparison of DFT and CCSD dipole moments, polarizabilities and hyperpolarizabilities

Cited by 19 publications

References 44 publications

Nonlinear Optical Properties of Thiolate-Protected Gold Clusters: A Theoretical Survey of the First Hyperpolarizabilities

Nonlinear Optical Properties of Thiolate-Protected Gold Clusters: A Theoretical Survey of the First Hyperpolarizabilities

Self-Consistent Auxiliary Density Perturbation Theory

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

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