Skip to main content
Article
Analytic Gradient for Density Functional Theory Based on the Fragment Molecular Orbital Method
Journal of Chemical Theory and Computation
  • Kurt Ryan Brorsen, Iowa State University
  • Federico Zahariev, Iowa State University
  • Hiroya Nakata, Tokyo Institute of Technology
  • Dmitri G. Fedorov, National Institute of Advanced Industrial Science and Technology
  • Mark S. Gordon, Iowa State University
Document Type
Article
Disciplines
Publication Version
Published Version
Publication Date
10-1-2014
DOI
10.1021/ct500808p
Abstract

The equations for the response terms for the fragment molecular orbital (FMO) method interfaced with the density functional theory (DFT) gradient are derived and implemented. Compared to the previous FMO–DFT gradient, which lacks response terms, the FMO–DFT analytic gradient has improved accuracy for a variety of functionals, when compared to numerical gradients. The FMO–DFT gradient agrees with the fully ab initio DFT gradient in which no fragmentation is performed, while reducing the nonlinear scaling associated with standard DFT. Solving for the response terms requires the solution of the coupled perturbed Kohn–Sham (CPKS) equations, where the CPKS equations are solved through a decoupled Z-vector procedure called the self-consistent Z-vector method. FMO–DFT is a nonvariational method and the FMO–DFT gradient is unique compared to standard DFT gradients in that the FMO–DFT gradient requires terms from both DFT and time-dependent density functional theory (TDDFT) theories.

Comments

Reprinted (adapted) with permission from Journal of Chemical Theory and Computation 10 (2014): 5297, doi:10.1021/ct500808p. Copyright 2014 American Chemical Society.

Copyright Owner
American Chemical Society
Language
en
File Format
application/pdf
Citation Information
Kurt Ryan Brorsen, Federico Zahariev, Hiroya Nakata, Dmitri G. Fedorov, et al.. "Analytic Gradient for Density Functional Theory Based on the Fragment Molecular Orbital Method" Journal of Chemical Theory and Computation Vol. 10 Iss. 12 (2014) p. 5297 - 5307
Available at: http://works.bepress.com/mark_gordon/374/