Block deformation analysis: Density matrix blocks as intramolecular deformation density

Abstract

Block deformation analysis as deformation density of atomic orbitals is introduced to analyze intramolecular interactions. In this respect, density matrix blocks in terms of natural atomic orbitals are employed to find interacting and noninteracting multicenter subsystem and extract the corresponding deformation density. Eigenanalysis of this deformation density is performed to result eigenvalues and eigenorbitals as displaced charge due to the intramolecular interaction and orbital space responsible for charge reorganization, respectively, that possesses advantages of other methods, simultaneously. It is applied to several small molecules, different types of carbon allotropes including zero-, one-, and two-dimensional nanostructures, and challenging systems such as ortho-hydrogen atoms in planar biphenyl. Results highly correlate with delocalization and Wiberg bond indices and show that eigenvalues of block deformation analysis deserved to be considered as bonding index.

Gas-Phase Interaction of CO, CO2, H2S, NH3, NO, NO2, and SO2 with Zn12O12 and Zn24 Atomic Clusters

“…The WBI is the addition of the square of an off-diagonal density matrix element between the atoms, and it is determined as follows WBI = prefix∑ K P jk 2 = 2 P jj − P jk 2 where P jk represents the density matrix element and P jj the changing density in the atomic orbital. There is no significant difference between the net bonding or anti-bonding type of element of the density matrix in the WBI …”

“…There is no significant difference between the net bonding or anti-bonding type of element of the density matrix in the WBI. 60 …”

Asymmetric electronic deformation in graphene molecular capacitors

“…For all types of deformation densities, spectral decomposition of $$$ \Delta \rho $$$ can be grouped into two components concerning the corresponding eigenvalues' signs [67–70]. When analyzing deformation density, the eigenvalues have a special characteristic that allows for assigning eigenorbitals to specific occurrences.…”

“…One of the major topics in the field of computational molecular electronics is analyzing charge distribution and its response to external electric field and several techniques are developed to analyze how these two components react to the applied voltage [10,63,64]. Also, electronic deformation density analysis is conducted for many chemical systems by present author including intermolecular and steric interaction analysis [65,66], capacitance of bilayer graphene flakes [30,60], and interatomic interaction [67]. In this respect, it has been shown that electronic deformations density can be used to analyze response of charge density to applied voltage [10].…”