Picture change error in quasirelativistic electron/spin density, Laplacian and bond critical points

• Published in: Chemical physics 2014-06, Vol.438, p.37-47
• Main Authors: Bučinský, Lukáš, Kucková, Lenka, Malček, Michal, Kožíšek, Jozef, Biskupič, Stanislav, Jayatilaka, Dylan, Büchel, Gabriel E., Arion, Vladimir B.
• Format: Article
• Language: English
• Subjects: 2-Component; Bond critical point; Electron density; Laplacian; Picture change error
• ISSN: 0301-0104
• DOI: 10.1016/j.chemphys.2014.04.013

[Display omitted] •Quasirelativistic study of electron density topology of Os and Ru complexes.•Electron/spin densities and negative Laplacian of electron density presented.•Analytic correction of picture change error at IOTC level.•Relativistic and spin–orbit effects are considered, IOTC vs. DKH2 compared. The change of picture of the quasirelativistic Hartree–Fock wave functions is considered for electron/spin densities, the negative Laplacian of electron density and the appropriate bond critical point characteristics from the Quantum Theory of Atoms In Molecules (QTAIM). [OsCl5(Hpz)]− and [RuCl5(NO)]2− transition metal complexes are considered. Both, scalar relativistic and spin–orbit effects have been accounted for using the Infinite Order Two Component (IOTC) Hamiltonian. Picture change error (PCE) correction in the electron and spin densities and the Laplacian of electron density are treated analytically. Generally, PCE is found significant only in the core region of the atoms for the electron/spin density as well as Laplacian.