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Analytical Gradients for Density Functional Calculations with Approximate Spin Projection

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Saito,  Toru
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Saito, T., & Thiel, W. (2012). Analytical Gradients for Density Functional Calculations with Approximate Spin Projection. The Journal of Physical Chemistry A, 116(40), 10864-10869. doi:10.1021/jp308916s.


Cite as: https://hdl.handle.net/11858/00-001M-0000-000E-E6CB-9
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.