skip to main content

Title: Certification and the potential energy landscape

Typically, there is no guarantee that a numerical approximation obtained using standard nonlinear equation solvers is indeed an actual solution, meaning that it lies in the quadratic convergence basin. Instead, it may lie only in the linear convergence basin, or even in a chaotic region, and hence not converge to the corresponding stationary point when further optimization is attempted. In some cases, these non-solutions could be misleading. Proving that a numerical approximation will quadratically converge to a stationary point is termed certification. In this report, we provide details of how Smale's α-theory can be used to certify numerically obtained stationary points of a potential energy landscape, providing a mathematical proof that the numerical approximation does indeed correspond to an actual stationary point, independent of the precision employed.
Authors:
 [1] ;  [2] ;  [1] ;  [3]
  1. Department of Mathematics, North Carolina State University, Raleigh, North Carolina 27695 (United States)
  2. (United Kingdom)
  3. Department of Chemistry, The University of Cambridge, Cambridge CB2 1EW (United Kingdom)
Publication Date:
OSTI Identifier:
22420085
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 22; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 97 MATHEMATICAL METHODS AND COMPUTING; ACCURACY; APPROXIMATIONS; EQUATIONS; MATHEMATICAL SOLUTIONS; POTENTIAL ENERGY