Adaptive algorithm for electronic structure calculations using reduction of Gaussian mixtures

DOI10.1098/RSPA.2018.0901MaRDI QIDQ5160686zbMATH OpenOpenAlexFDO

Authors Gregory Beylkin, Lucas Monzón, Xinshuo Yang

Publication date 29 October 2021

Published in Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences (Search for Journal in Brave)

Full work available at URL https://arxiv.org/abs/1812.09284

zbMATH Keywords

adaptive algorithmscomputational chemistrycomputational mathematicselectronic structureintegral equationsmultivariate Gaussian mixturesreduction ofmultivariate mixtures

Mathematics Subject Classification ID

Classical flows, reactions, etc. in chemistry (92E20)

Abstract: We present a new adaptive method for electronic structure calculations based on novel fast algorithms for reduction of multivariate mixtures. In our calculations, spatial orbitals are maintained as Gaussian mixtures whose terms are selected in the process of solving equations. Using a fixed basis leads to the so-called "basis error" since orbitals may not lie entirely within the linear span of the basis. To avoid such an error, multiresolution bases are used in adaptive algorithms so that basis functions are selected from a fixed collection of functions, large enough as to approximate solutions within any user-selected accuracy. Our new method achieves adaptivity without using a multiresolution basis. Instead, as a part of an iteration to solve nonlinear equations, our algorithm selects the "best" subset of linearly independent terms of a Gaussian mixture from a collection that is much larger than any possible basis since the locations and shapes of the Gaussian terms are not fixed in advance. Approximating an orbital within a given accuracy, our algorithm yields significantly fewer terms than methods using multiresolution bases. We demonstrate our approach by solving the Hartree-Fock equations for two diatomic molecules, HeH+ and LiH, matching the accuracy previously obtained using multiwavelet bases.

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Cited in

(4)

• Reduction of multivariate mixtures and its applications
• An Adaptive Multiscale Approach for Electronic Structure Methods
• Rapid filtration algorithm to construct a minimal basis on the fly from a primitive Gaussian basis
• On representations of the Helmholtz Green's function

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