skip to main content

DOE PAGESDOE PAGES

Title: Matrix Methods for Solving Hartree-Fock Equations in Atomic Structure Calculations and Line Broadening

Atomic structure of N-electron atoms is often determined by solving the Hartree-Fock equations, which are a set of integro-differential equations. The integral part of the Hartree-Fock equations treats electron exchange, but the Hartree-Fock equations are not often treated as an integro-differential equation. The exchange term is often approximated as an inhomogeneous or an effective potential so that the Hartree-Fock equations become a set of ordinary differential equations (which can be solved using the usual shooting methods). Because the Hartree-Fock equations are an iterative-refinement method, the inhomogeneous term relies on the previous guess of the wavefunction. In addition, there are numerical complications associated with solving inhomogeneous differential equations. This work uses matrix methods to solve the Hartree-Fock equations as an integro-differential equation. It is well known that a derivative operator can be expressed as a matrix made of finite-difference coefficients; energy eigenvalues and eigenvectors can be obtained by using linear-algebra packages. The integral (exchange) part of the Hartree-Fock equation can be approximated as a sum and written as a matrix. The Hartree-Fock equations can be solved as a matrix that is the sum of the differential and integral matrices. We compare calculations using this method against experiment and standard atomic structuremore » calculations. This matrix method can also be used to solve for free-electron wavefunctions, thus improving how the atoms and free electrons interact. Here, this technique is important for spectral line broadening in two ways: it improves the atomic structure calculations, and it improves the motion of the plasma electrons that collide with the atom.« less
Authors:
 [1] ;  [1] ;  [2] ; ORCiD logo [2] ;  [1] ;  [3] ;  [3]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of Texas at Austin, Austin, TX (United States)
Publication Date:
Report Number(s):
SAND-2018-2057J
Journal ID: ISSN 2218-2004; ATOMC5; 660952
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Atoms
Additional Journal Information:
Journal Volume: 6; Journal Issue: 2; Journal ID: ISSN 2218-2004
Publisher:
MDPI
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; atomic structure; hartree fock; exchange; line broadening; scattering
OSTI Identifier:
1457406

Gomez, Thomas, Nagayama, Taisuke, Fontes, Chris, Kilcrease, Dave, Hansen, Stephanie B., Montgomery, Mike, and Winget, Don. Matrix Methods for Solving Hartree-Fock Equations in Atomic Structure Calculations and Line Broadening. United States: N. p., Web. doi:10.3390/atoms6020022.
Gomez, Thomas, Nagayama, Taisuke, Fontes, Chris, Kilcrease, Dave, Hansen, Stephanie B., Montgomery, Mike, & Winget, Don. Matrix Methods for Solving Hartree-Fock Equations in Atomic Structure Calculations and Line Broadening. United States. doi:10.3390/atoms6020022.
Gomez, Thomas, Nagayama, Taisuke, Fontes, Chris, Kilcrease, Dave, Hansen, Stephanie B., Montgomery, Mike, and Winget, Don. 2018. "Matrix Methods for Solving Hartree-Fock Equations in Atomic Structure Calculations and Line Broadening". United States. doi:10.3390/atoms6020022. https://www.osti.gov/servlets/purl/1457406.
@article{osti_1457406,
title = {Matrix Methods for Solving Hartree-Fock Equations in Atomic Structure Calculations and Line Broadening},
author = {Gomez, Thomas and Nagayama, Taisuke and Fontes, Chris and Kilcrease, Dave and Hansen, Stephanie B. and Montgomery, Mike and Winget, Don},
abstractNote = {Atomic structure of N-electron atoms is often determined by solving the Hartree-Fock equations, which are a set of integro-differential equations. The integral part of the Hartree-Fock equations treats electron exchange, but the Hartree-Fock equations are not often treated as an integro-differential equation. The exchange term is often approximated as an inhomogeneous or an effective potential so that the Hartree-Fock equations become a set of ordinary differential equations (which can be solved using the usual shooting methods). Because the Hartree-Fock equations are an iterative-refinement method, the inhomogeneous term relies on the previous guess of the wavefunction. In addition, there are numerical complications associated with solving inhomogeneous differential equations. This work uses matrix methods to solve the Hartree-Fock equations as an integro-differential equation. It is well known that a derivative operator can be expressed as a matrix made of finite-difference coefficients; energy eigenvalues and eigenvectors can be obtained by using linear-algebra packages. The integral (exchange) part of the Hartree-Fock equation can be approximated as a sum and written as a matrix. The Hartree-Fock equations can be solved as a matrix that is the sum of the differential and integral matrices. We compare calculations using this method against experiment and standard atomic structure calculations. This matrix method can also be used to solve for free-electron wavefunctions, thus improving how the atoms and free electrons interact. Here, this technique is important for spectral line broadening in two ways: it improves the atomic structure calculations, and it improves the motion of the plasma electrons that collide with the atom.},
doi = {10.3390/atoms6020022},
journal = {Atoms},
number = 2,
volume = 6,
place = {United States},
year = {2018},
month = {4}
}

Works referenced in this record:

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965