Approximate Spin Projected Spin-Unrestricted Density Functional Theory Method: Application to Diradical Character Dependences of Second Hyperpolarizabilities

摘要

We develop a novel method for the calculation and the analysis of the one-electron reduced densities in openshell molecular systems using the natural orbitals and approximate spin projected occupation numbers obtained from broken symmetry (BS), i.e., spin-unrestricted (U), density functional theory (DFT) calculations. The performance of this approximate spin projection (ASP) scheme is examined for the diradical character dependence of the second hyperpolarizability (γ) using several exchange-correlation functionals, i.e., hybrid and long-range corrected UDFT schemes. It is found that the ASP-LC-UBLYP method with a range separating parameter μ = 0.47 reproduces semiquantitatively the strongly-correlated [UCCSD(T)] result for p-quinodimethane, i.e., the γ variation as a function of the diradical character.