fast and accurate algorithm for QTAIM integration in solids

• Published in: Journal of computational chemistry 2011-01, Vol.32 (2), p.291-305
• Main Authors: Otero-de-la-Roza, A, Luaña, Víctor
• Format: Article
• Language: English
• Subjects: Accuracy; Algorithms; atomic properties in solids; Atoms & subatomic particles; atoms in molecules; Crystal structure; integration grid; Molecular structure; octree; QTAIM; Quantum theory; Solids
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.21620

A new algorithm is presented for the calculation of atomic properties, in the sense of the quantum theory of atoms in molecules. This new method, named QTREE, applies to solid-state densities and allows the computation of the atomic properties of all the atoms in the crystal in seconds to minutes. The basis of the method is the recursive subdivision of a symmetry-reduced wedge of the Wigner-Seitz cell, which in turn is expressed as a union of tetrahedra, plus the use of β-spheres to improve the performance. A considerable speedup is thus achieved compared with traditional quadrature-based schemes, justified by the poor performance of the latter because of the particular features of atomic basins in solids. QTREE can use both analytical or interpolated densities, calculates all the atomic properties available, and converges to the correct values in the limit of infinite precision. Several gradient path tracing and integration techniques are tested. Basin volumes and charges for a selected set of 11 crystals are determined as a test of the new method.