arXiv2023
The importance of Localized Molecular Orbitals in correlation treatments beyond mean-field calculation and in the illustration of chemical bonding can hardly be overstated. However, generation of orthonormal localized occupied MOs is significantly more straightforward than obtaining orthonormal localized virtual MOs. Orthonormal molecular orbitals allow facile use of highly efficient group theoretical methods for calculation of Hamiltonian matrix elements in multireference configuration interaction calculations and in quasidegenerate perturbation treatments, such as the GVVPT2 Theory. Moreover, localized MOs can elucidate qualitative understanding of bonding in molecules, in addition to high accuracy quantitative descriptions. We adopt the powers of the fourth moment cost function introduced by Jørgensen and coworkers. Because the fourth moment cost functions are prone to having multiple negative Hessian eigenvalues when starting from easily available canonical MOs, standard optimization algorithms can fail to obtain the orbitals of the virtual or partially occupied spaces. To overcome this drawback, we applied a Trust Region algorithm on an orthonormal Riemannian manifold with an approximate retraction from the tangent space built into first and second derivatives of the cost function. Moreover, the Riemannian Trust Region outer iterations were coupled to truncated conjugate gradient inner loops, which avoided any costly solutions of simultaneous linear equations or eigenvector/eigenvalue solutions. Numerical examples are provided on model systems, including the high connectivity H10 set in 1-, 2- and 3-dimensional arrangements, and on a chemically realistic description of cyclobutadiene, and the propargyl radical. In addition to demonstrating the algorithm on occupied and virtual blocks of orbitals, the method is also shown to work on the active space at the MCSCF level of theory.