Strong Correlation in Acene Sheets from the Active-Space Variational Two-Electron Reduced Density Matrix Method: Effects of Symmetry and Size

Abstract

Polyaromatic hydrocarbons (PAHs) are a class of organic molecules with importance in several branches of science, including medicine, combustion chemistry, and materials science. The delocalized π-orbital systems in PAHs require highly accurate electronic structure methods to capture strong electron correlation. Treating correlation in PAHs has been challenging because (i) traditional wave function methods for strong correlation have not been applicable since they scale exponentially in the number of strongly correlated orbitals, and (ii) alternative methods such as the density-matrix renormalization group and variational two-electron reduced density matrix (2-RDM) methods have not been applied beyond linear acene chains. In this paper we extend the earlier results from active-space variational 2-RDM theory [Gidofalvi, G.; Mazziotti, D. A. J. Chem. Phys. 2008, 129, 134108] to the more general two-dimensional arrangement of rings--acene sheets--to study the relationship between geometry and electron correlation in PAHs. The acene-sheet calculations, if performed with conventional wave function methods, would require wave function expansions with as many as 1.5 × 10(17) configuration state functions. To measure electron correlation, we employ several RDM-based metrics: (i) natural-orbital occupation numbers, (ii) the 1-RDM von Neumann entropy, (iii) the correlation energy per carbon atom, and (iv) the squared Frobenius norm of the cumulant 2-RDM. The results confirm a trend of increasing polyradical character with increasing molecular size previously observed in linear PAHs and reveal a corresponding trend in two-dimensional (arch-shaped) PAHs. Furthermore, in PAHs of similar size they show significant variations in correlation with geometry. PAHs with the strictly linear geometry (chains) exhibit more electron correlation than PAHs with nonlinear geometries (sheets).