Localized orbitals for optimal decomposition of molecular properties

TL;DR

This paper introduces a parameter-free method for transforming delocalized molecular orbitals into localized, property-optimized orbitals that enable accurate decomposition of molecular properties into atomic and pairwise contributions.

Contribution

It presents a novel, parameter-free procedure for creating localized orbitals optimized for property decomposition, including the development of Chemist's LPOs and their implementation in JANPA.

Findings

High accuracy in property decomposition demonstrated on 33,432 molecules.

The methods are implemented in open-source software JANPA.

The approach provides chemically meaningful orbital localization.

Abstract

Localized orbitals are important for modeling and interpreting complicated electronic structures of atoms and molecules in a chemically meaningful way. Here, we present the parameter-free procedure for transforming delocalized molecular orbitals (either canonical self-consistent field orbitals, or Lowdin natural orbitals obtained from a general wavefunction) into the localized property-optimized orbitals (LPOs), which can be used for building the most accurate (in the Frobenius norm sense) approximation to the first-order reduced density matrix in form of the sum of localized mono- and diatomic terms. In this way any, any one-electron molecular property can be decomposed into contributions associated with individual atoms and the pairs of atoms, with the upper bound for the decomposition acucracy known in advance due to Cauchy-Bunyakovsky-Schwarz inequality. In addition, an algorithm is proposed for obtaining 'the Chemist's LPOs' (CLPOs) set of localized orbitals containing a single orbital per a pair of electrons and forming an idealized Lewis structure with the one-electron properties which are closest to the properties obtained from the original many-electron wavefunction. The computational algorithms for constructing LPOs and CLPOs as well as their underlying atomic hybrid orbitals (AHOs and LHOs respectively) from the results of quantum-chemical calculations are presented and their implementation within the open-source freeware program JANPA (http://janpa.sourceforge.net/ ) is discussed. The performance of the proposed orbital localization procedures is assessed using the test set of density matrices of 33432 small molecules obtained at Hartree-Fock and 2-nd order Moller-Plesset theory levels.