Extremely localized molecular orbitals (ELMO): a non-orthogonal Hartree-Fock method

A new optimization method fur extremely localized molecular orbitals (ELMO) is derived in a nonorthogonal formalism. The method is based on a quasi Newton-Raphson algorithm ill which an approximate diagonal-blocked Hessian matrix is calculated through the Fock matrix. The Hessian matrix inverse is updated at each iteration by a variable metric updating procedure to account for the intrinsically small coupling between the orbitals. The updated orbitals are obtained with approximately n(2) operations. No n(3) processes such as matrix diagonalization, matrix multiplication or orbital orthogonalization are employed. The use of localized orbitals allows for the creation of high-quality initial ''guess'' orbitals from optimized molecular orbitals of small systems and thus reduces the number of iterations to converge. The delocalization effects are included by a Jacobi correction (JC) which allows the accurate calculation of the total energy with a limited number of operations. This extension, referred to as ELMO(JC). is a variational method that reproduces the Hartree-Fock (HF) energy with an error of less than 2 kcal/mol for a I-educed total cost compared to standard HF methods. The small number of variables, even for a very large system, and the limited number of operations potentially makes ELMO a method of choice to study large systems.