DOE OSTI2020
Symmetry is a fundamental concept that plays a critical role in many chemical and physical phenomena and processes, which highlights the importance of theoretical methods to correctly handle symmetry. The recently developed localized orbital scaling correction (LOSC1) shows great improvement on the description of band gaps, photoemission spectra, and dissociation limits of cationic species. However, issues remain with LOSC1 in dealing with the symmetry and degeneracy of electronic states, which are also relevant to other methods using localization. In this work, we utilize a new method that deals with the physical-space and the energy-space localization on an equal footing. The resulting localized orbitals, i.e., orbitalets, are able to maintain more symmetry and the desired state degeneracy, which is important in calculating the electronic structure of both molecules and periodic bulk systems. Furthermore, the curvature matrix is redefined to improve potential energy curves for systems with stretched bonds, while retaining the correct dissociation limits. This new approach, termed LOSC2, includes only two fitting parameters. It maintains accuracy similar to that of LOSC1 over many properties, while overcoming LOSC1’s deficiencies in symmetry and degeneracy. Our tests have shown that LOSC2 orbitalets possess the full- or subgroup of molecular symmetry if allowed, which preserves the state degeneracy. Tests on differently sized planar annulenes, odd-numbered allenes, and triphenylene again verify that LOSC2 is able to maintain the state degeneracy, while LOSC1 cannot. Finally, all the tests demonstrate the advantage of LOSC2 in the calculation of molecular systems and its potential for application to periodic bulk systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗