Atomic effective potentials for starting molecular electronic structure calculations

Laikov, Dimitri N.; Briling, Ksenia R.

doi:10.1007/s00214-019-2521-3

Cited by 10 publications

(14 citation statements)

References 38 publications

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“…Interestingly, the errors for the present fits compare favorably with those for the optimized fits of ref. 9: the accuracy of the present unoptimized fits is close to that of the hand-optimized potentials of ref. 9.…”

Section: Error-function Fits Of the Local Exchange Potentialsupporting

confidence: 81%

“…9: the accuracy of the present unoptimized fits is close to that of the hand-optimized potentials of ref. 9. It is also interesting to note that the mean errors for all of the Gaussian-fit potentials (in the range of 11 to 16 kcal/mol) are close to those of the other choices for the fully numerical potential in the quadrature study in table II (10 to 16 kcal/mol).…”

Section: Error-function Fits Of the Local Exchange Potentialsupporting

confidence: 81%

“…1 and 4 has also been recently suggested in ref. 9, in which a universal atomic potential is employed as in ref. 1, but instead of real-space calculations at the basis set limit the potentials are obtained for a small Gaussian basis set and biased for molecular calculations on the lines of ref.…”

Section: Introductionmentioning

confidence: 99%

“…However, the optimization in ref. 9 was restricted to fixing the wrong asymptotic behavior of the optimized effective potential discussed by one of the present authors in ref. 10, and instead of minimizing the resulting guess energy as Whitten and coworkers in refs.…”

Section: Introductionmentioning

confidence: 99%

“…4-6, the procedure of ref. 9 maximizes the overlap of the guess orbitals onto the SCF solution according to the procedure first introduced in ref. 1. All variants of SAP (including refs.…”

Section: Introductionmentioning

confidence: 99%

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Efficient implementation of the superposition of atomic potentials initial guess for electronic structure calculations in Gaussian basis sets

Lehtola

Visscher

Engel

2020

The Journal of Chemical Physics

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The superposition of atomic potentials (SAP) approach has recently been shown to be a simple and efficient way to initialize electronic structure calculations [S. Lehtola, J. Chem. Theory Comput. 15, 1593].Here, we study the differences between effective potentials from fully numerical density functional and optimized effective potential calculations for fixed configurations. We find that the differences are small, overall, and choose exchange-only potentials at the local density approximation level of theory computed on top of Hartree-Fock densities as a good compromise. The differences between potentials arising from different atomic configurations are also found to be small at this level of theory.Furthermore, we discuss the efficient Gaussian-basis implementation of SAP via error function fits to fully numerical atomic radial potentials. The guess obtained from the fitted potentials can be easily implemented in any Gaussian-basis quantum chemistry code in terms of two-electron integrals. Fits covering the whole periodic table from H to Og are reported for non-relativistic as well as fully relativistic four-component calculations that have been carried out with fully numerical approaches.

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Section: Error-function Fits Of the Local Exchange Potentialsupporting

confidence: 81%

Section: Error-function Fits Of the Local Exchange Potentialsupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…4-6, the procedure of ref. 9 maximizes the overlap of the guess orbitals onto the SCF solution according to the procedure first introduced in ref. 1. All variants of SAP (including refs.…”

Section: Introductionmentioning

confidence: 99%

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Efficient implementation of the superposition of atomic potentials initial guess for electronic structure calculations in Gaussian basis sets

Lehtola

Visscher

Engel

2020

The Journal of Chemical Physics

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Multilevel approach to the initial guess for self‐consistent field calculations

Hégely

Kállay

2021

Int J of Quantum Chemistry

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A new multilevel approach is presented to the initial guess for self-consistent field (SCF) calculations, which combines the superposition of atomic densities (SAD) procedure and the density matrix of a semi-empirical quantum mechanics (SQM) calculation through projection. The proposed initial guess method produces a polarized, spin-specific initial density, while its computational costs are a few orders of magnitude lower than the expenses of a scheme that projects the density matrix of a standard quantum chemical calculation utilizing a minimal AO basis set (pMIN). The projected SQM density-based (pSQM) technique is thoroughly tested using the GFN2-xTB approach, and its efficiency and reliability are compared with those of the standard SAD and density matrix projection techniques. The results indicate that the calculations using the pSQM scheme require somewhat fewer SCF iteration steps compared with the SAD method, however, the SAD, the pSQM, and the pMIN techniques have similar performance.

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SPA^HM(a,b): Encoding the Density Information from Guess Hamiltonian in Quantum Machine Learning Representations

Briling,

Calvino Alonso,

Fabrizio

et al. 2024

J. Chem. Theory Comput.

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Recently, we introduced a class of molecular representations for kernel-based regression methods�the spectrum of approximated Hamiltonian matrices (SPA H M)�that takes advantage of lightweight one-electron Hamiltonians traditionally used as a self-consistent field initial guess. The original SPA H M variant is built from occupied-orbital energies (i.e., eigenvalues) and naturally contains all of the information about nuclear charges, atomic positions, and symmetry requirements. Its advantages were demonstrated on data sets featuring a wide variation of charge and spin, for which traditional structure-based representations commonly fail. SPA H M(a,b), as introduced here, expand the eigenvalue SPA H M into local and transferable representations. They rely upon one-electron density matrices to build fingerprints from atomic and bond density overlap contributions inspired from preceding state-of-the-art representations. The performance and efficiency of SPA H M(a,b) is assessed on the predictions for data sets of prototypical organic molecules (QM7) of different charges and azoheteroarene dyes in an excited state. Overall, both SPA H M(a) and SPA H M(b) outperform state-of-the-art representations on difficult prediction tasks such as the atomic properties of charged open-shell species and of π-conjugated systems.

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Atomic effective potentials for starting molecular electronic structure calculations

Cited by 10 publications

References 38 publications

Efficient implementation of the superposition of atomic potentials initial guess for electronic structure calculations in Gaussian basis sets

Efficient implementation of the superposition of atomic potentials initial guess for electronic structure calculations in Gaussian basis sets

Multilevel approach to the initial guess for self‐consistent field calculations

SPA^HM(a,b): Encoding the Density Information from Guess Hamiltonian in Quantum Machine Learning Representations

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Atomic effective potentials for starting molecular electronic structure calculations

Cited by 10 publications

References 38 publications

Efficient implementation of the superposition of atomic potentials initial guess for electronic structure calculations in Gaussian basis sets

Efficient implementation of the superposition of atomic potentials initial guess for electronic structure calculations in Gaussian basis sets

Multilevel approach to the initial guess for self‐consistent field calculations

SPAHM(a,b): Encoding the Density Information from Guess Hamiltonian in Quantum Machine Learning Representations

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Product

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SPA^HM(a,b): Encoding the Density Information from Guess Hamiltonian in Quantum Machine Learning Representations