Funct. Mater. 2022; 29 (3): 408-418.

doi:https://doi.org/10.15407/fm29.03.408

Using Brillouin's theorem for obtaining symmetry-preserving and symmetry-breaking solutions. Application to graphene quantum dots

A.V.Luzanov

STC "Institute for Single Crystals", National Academy of Sciences of Ukraine, 60 Lenin Ave., 61001 Kharkiv, Ukraine

Abstract: 

The consistent Brillouin-theorem-based scheme is developed for obtaining numerical Hartree-Fock (HF) solutions at the semiempirical level. Our approach for getting corresponding HF results exploits a general configurational interaction singles procedure for which the compact formulation via only one-electron matrices in AO basis set is applied. The proposed algorithms demonstrate their reliability and feasibility for large-scale conjugated molecules. Particular focus is on finding HF symmetry-preserving and symmetry-breaking solutions of the charge density wave (CDW) type. Among the main systems studied here are graphene quantum dots of periacene type and singlet polyradical structures consisting of triangulene subunits (particularly, π-system of the recently synthesized triangulenic "nanostar") We show that formally incorrect HF solutions of CDW type (occurence of atomic net charges) implicitly reflect a decrease of atomic valencies in highly correlated alternant π-structures.

Keywords: 
configurational interaction, Hartree-Fock convergence and stability, graphene-like molecules, alternant symmety, π-electrons.

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