Double hybrid <scp>DFT</scp> calculations with Slater type orbitals

Förster, A.; Visscher, Lucas

doi:10.1002/jcc.26209

Cited by 25 publications

(26 citation statements)

References 308 publications

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“…We will also consider a set of radical (open-shell) small molecular systems, taken from the last work of Loos et al, 52 emitting diodes to circumvent the difficulty in harvesting triplet excitons, typical of closed-shell emitters. 53,54 Since DH functionals are being progressively and successfully implemented in widely used codes, 55,56 we hope this assessment will further stimulate both the development and the use of such methods for excited-state applications, as their accuracy for all kind of excitation energies is confirmed.…”

Section: Introductionmentioning

confidence: 96%

Assessing challenging intra‐ and inter‐molecular charge‐transfer excitations energies with double‐hybrid density functionals

et al. 2021

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We investigate the performance of a set of recently introduced range-separated double-hybrid functionals, namely ωB2-PLYP, ωB2GP-PLYP, RSX-0DH, and RSX-QIDH models for hard-to-calculate excitation energies. We compare with the parent (B2-PLYP, B2GP-PLYP, PBE0-DH, and PBE-QIDH) and other (DSD-PBEP86) doublehybrid models as well as with some of the most widely employed hybrid functionals (B3LYP, PBE0, M06-2X, and ωB97X). For this purpose, we select a number of medium-sized intra-and inter-molecular charge-transfer excitations, which are known to be challenging to calculate using time-dependent density-functional theory (TD-DFT) and for which accurate reference values are available. We assess whether the high accuracy shown by the newest double-hybrid models is also confirmed for those cases too. We find that asymptotically corrected double-hybrid models yield a superior performance, especially for the inter-molecular charge-transfer excitation energies, as compared to standard double-hybrid models. Overall, the PBE-QIDH and its corresponding range-separated RSX-QIDH functional are recommended for general-purpose TD-DFT applications, depending on whether long-range effects are expected to play a significant role.

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Section: Introductionmentioning

confidence: 96%

Assessing challenging intra‐ and inter‐molecular charge‐transfer excitations energies with double‐hybrid density functionals

et al. 2021

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“… 158 , 159 It has also been applied to correlated methods and shown to be very accurate when appropriate auxiliary fit sets are used. 160 − 163 …”

Section: Introductionmentioning

confidence: 99%

Low-Order Scaling G₀W₀ by Pair Atomic Density Fitting

Förster

Visscher

2020

J. Chem. Theory Comput.

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172

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We derive a low-scaling G 0 W 0 algorithm for molecules using pair atomic density fitting (PADF) and an imaginary time representation of the Green’s function and describe its implementation in the Slater type orbital (STO)-based Amsterdam density functional (ADF) electronic structure code. We demonstrate the scalability of our algorithm on a series of water clusters with up to 432 atoms and 7776 basis functions and observe asymptotic quadratic scaling with realistic threshold qualities controlling distance effects and basis sets of triple-ζ (TZ) plus double polarization quality. Also owing to a very small prefactor, a G 0 W 0 calculation for the largest of these clusters takes only 240 CPU hours with these settings. We assess the accuracy of our algorithm for HOMO and LUMO energies in the GW100 database. With errors of 0.24 eV for HOMO energies on the quadruple-ζ level, our implementation is less accurate than canonical all-electron implementations using the larger def2-QZVP GTO-type basis set. Apart from basis set errors, this is related to the well-known shortcomings of the GW space-time method using analytical continuation techniques as well as to numerical issues of the PADF approach of accurately representing diffuse atomic orbital (AO) products. We speculate that these difficulties might be overcome by using optimized auxiliary fit sets with more diffuse functions of higher angular momenta. Despite these shortcomings, for subsets of medium and large molecules from the GW5000 database, the error of our approach using basis sets of TZ and augmented double-ζ (DZ) quality is decreasing with system size. On the augmented DZ level, we reproduce canonical, complete basis set limit extrapolated reference values with an accuracy of 80 meV on average for a set of 20 large organic molecules. We anticipate our algorithm, in its current form, to be very useful in the study of single-particle properties of large organic systems such as chromophores and acceptor molecules.

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“…The Laplace transform (LT) technique 29 , 30 proposed by Almlöf to eliminate the energy denominator of MP2 has also become fundamental to reduce the fifth-power-scaling computational complexity of MP2. 31 − 39 Aiming toward the same goal, the particularly simple form of MP2 was also utilized in a number of creative developments on the basis of, for instance, Cholesky-decomposed pseudo-density matrices; 40 − 43 stochastic, 44 , 45 quadrature-based, 46 and pseudospectral 47 , 48 approaches; nonorthogonal 49 , 50 or Slater-type orbitals; 51 , 52 tensor hypercontraction; 53 , 54 as well as large-scale parallelization. 35 , 55 , 56 …”

Section: Introductionmentioning

confidence: 99%

Linear-Scaling Open-Shell MP2 Approach: Algorithm, Benchmarks, and Large-Scale Applications

Szabó

Csóka

Kállay

et al. 2021

J. Chem. Theory Comput.

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A linear-scaling local second-order Møller–Plesset (MP2) method is presented for high-spin open-shell molecules based on restricted open-shell (RO) reference functions. The open-shell local MP2 (LMP2) approach inherits the iteration- and redundancy-free formulation and the completely integral-direct, OpenMP-parallel, and memory and disk use economic algorithms of our closed-shell LMP2 implementation. By utilizing restricted local molecular orbitals for the demanding integral transformation step and by introducing a novel long-range spin-polarization approximation, the computational cost of RO-LMP2 approaches that of closed-shell LMP2. Extensive benchmarks were performed for reactions of radicals, ionization potentials, as well as spin-state splittings of carbenes and transition-metal complexes. Compared to the conventional MP2 reference for systems of up to 175 atoms, local errors of at most 0.1 kcal/mol were found, which are well below the intrinsic accuracy of MP2. RO-LMP2 computations are presented for challenging protein models of up to 601 atoms and 11 000 basis functions, which involve either spin states of a complexed iron ion or a highly delocalized singly occupied orbital. The corresponding runtimes of 9–15 h obtained with a single, many-core CPU demonstrate that MP2, as well as spin-scaled MP2 and double-hybrid density functional methods, become widely accessible for open-shell systems of unprecedented size and complexity.

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Double hybrid DFT calculations with Slater type orbitals

Cited by 25 publications

References 308 publications

Assessing challenging intra‐ and inter‐molecular charge‐transfer excitations energies with double‐hybrid density functionals

Assessing challenging intra‐ and inter‐molecular charge‐transfer excitations energies with double‐hybrid density functionals

Low-Order Scaling G₀W₀ by Pair Atomic Density Fitting

Linear-Scaling Open-Shell MP2 Approach: Algorithm, Benchmarks, and Large-Scale Applications

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Double hybrid DFT calculations with Slater type orbitals

Cited by 25 publications

References 308 publications

Assessing challenging intra‐ and inter‐molecular charge‐transfer excitations energies with double‐hybrid density functionals

Assessing challenging intra‐ and inter‐molecular charge‐transfer excitations energies with double‐hybrid density functionals

Low-Order Scaling G0W0 by Pair Atomic Density Fitting

Linear-Scaling Open-Shell MP2 Approach: Algorithm, Benchmarks, and Large-Scale Applications

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Low-Order Scaling G₀W₀ by Pair Atomic Density Fitting