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Analytical gradients for density functional calculations with approximate spin projection.

Authors
  • Saito, Toru
  • Thiel, Walter
Type
Published Article
Journal
The Journal of Physical Chemistry A
Publisher
American Chemical Society
Publication Date
Nov 08, 2012
Volume
116
Issue
44
Pages
10864–10869
Identifiers
DOI: 10.1021/jp308916s
PMID: 23088261
Source
Medline
License
Unknown

Abstract

We have derived and implemented analytical gradients for broken-symmetry unrestricted density functional calculations (BS-UDFT) with removal of spin contamination by Yamaguchi's approximate spin projection method. Geometry optimizations with these analytical gradients (AGAP-opt) yield results consistent with those obtained with the previously available numerical gradients (NAP-opt). The AGAP-opt approach is found to be more precise, efficient, and robust than NAP-opt. It allows full geometry optimizations for large open-shell systems. We report results for three types of organic diradicals and for a binuclear vanadium(II) complex to demonstrate the merits of removing the spin contamination effects during geometry optimization (AGAP-opt vs BS-UDFT) and to illustrate the superior performance of the analytical gradients (AGAP-opt vs NAP-opt). The results for the vanadium(II) complex indicate that the AGAP-opt method is capable of handling pronounced spin contamination effects in large binuclear transition metal complexes with two magnetic centers.

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