TY - JOUR

T1 - Downward quantum learning from element 118

T2 - Automated generation of Fermi-Löwdin orbitals for all atoms

AU - Pederson, Mark R.

AU - Johnson, Alexander I.

AU - Withanage, Kushantha P.K.

AU - Dolma, Sherab

AU - Flores, Gustavo Bravo

AU - Hooshmand, Zahra

AU - Khandal, Kusal

AU - Lasode, Peter O.

AU - Baruah, Tunna

AU - Jackson, Koblar A.

N1 - Funding Information:
A.I.J., K.P.K.W., T.B., K.A.J., and M.R.P.’s contribution to this work was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DOE-BES), as part of the Computational Chemical Sciences Program, under Award No. DE-SC0018331. Z.H. was supported by the DOE-BES MQM EFRC under Award No. DE-SC0019330. G.B.F. and S.D. were supported by the PNNL LDRD project (Project No. 209668, NM1103) and the University of Texas at El Paso. P.O.L. and K.K. were supported by the University of Texas at El Paso. The calculations were carried out on the JAKAR supercomputer at the University of Texas at El Paso and on compute nodes at the Institute for Cyber-Enabled Research at Michigan State University provided by the Central Michigan University. 2
Publisher Copyright:
© 2023 Author(s).

PY - 2023/2/28

Y1 - 2023/2/28

N2 - A new algorithm based on a rigorous theorem and quantum data computationally mined from element 118 guarantees automated construction of initial Fermi-Löwdin-Orbital (FLO) starting points for all elements in the Periodic Table. It defines a means for constructing a small library of scalable FLOs for universal use in molecular and solid-state calculations. The method can be systematically improved for greater efficiency and for applications to excited states such as x-ray excitations and optically silent excitations. FLOs were introduced to recast the Perdew-Zunger self-interaction correction (PZSIC) into an explicit unitarily invariant form. The FLOs are generated from a set of N quasi-classical electron positions, referred to as Fermi-Orbital descriptors (FODs), and a set of N-orthonormal single-electron orbitals. FOD positions, when optimized, minimize the PZSIC total energy. However, creating sets of starting FODs that lead to a positive definite Fermi orbital overlap matrix has proven to be challenging for systems composed of open-shell atoms and ions. The proof herein guarantees the existence of a FLOSIC solution and further guarantees that if a solution for N electrons is found, it can be used to generate a minimum of N - 1 and a maximum of 2N - 2 initial starting points for systems composed of a smaller number of electrons. Applications to heavy and super-heavy atoms are presented. All starting solutions reported here were obtained from a solution for element 118, Oganesson.

AB - A new algorithm based on a rigorous theorem and quantum data computationally mined from element 118 guarantees automated construction of initial Fermi-Löwdin-Orbital (FLO) starting points for all elements in the Periodic Table. It defines a means for constructing a small library of scalable FLOs for universal use in molecular and solid-state calculations. The method can be systematically improved for greater efficiency and for applications to excited states such as x-ray excitations and optically silent excitations. FLOs were introduced to recast the Perdew-Zunger self-interaction correction (PZSIC) into an explicit unitarily invariant form. The FLOs are generated from a set of N quasi-classical electron positions, referred to as Fermi-Orbital descriptors (FODs), and a set of N-orthonormal single-electron orbitals. FOD positions, when optimized, minimize the PZSIC total energy. However, creating sets of starting FODs that lead to a positive definite Fermi orbital overlap matrix has proven to be challenging for systems composed of open-shell atoms and ions. The proof herein guarantees the existence of a FLOSIC solution and further guarantees that if a solution for N electrons is found, it can be used to generate a minimum of N - 1 and a maximum of 2N - 2 initial starting points for systems composed of a smaller number of electrons. Applications to heavy and super-heavy atoms are presented. All starting solutions reported here were obtained from a solution for element 118, Oganesson.

UR - http://www.scopus.com/inward/record.url?scp=85148879671&partnerID=8YFLogxK

U2 - 10.1063/5.0135089

DO - 10.1063/5.0135089

M3 - Article

AN - SCOPUS:85148879671

SN - 0021-9606

VL - 158

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 8

M1 - 084101

ER -