Polarization propagator theory and the entanglement between MO excitations

Abstract

Entanglement is at the core of quantum physics and so, one may conjecture that it should have some influence on atomic and molecular response properties. The usual way of treating entanglement is by applying information theory via the von Newman entropy. Given that the principal propagator is the operator that contains the physical information that arises due to the transmission of the effects of two external perturbations through the electronic framework of a quantum system, it should have in it the information necessary to quantify the likely entanglement among molecular orbital excitations. In this article we first propose a proper density matrix and from it, the way to quantify entangled excitations by using information theory. The NMR J-couplings are among the best candidates to learn about the potentialities of this formalism. We applied this new tool to analyze the famous Karplus rule and found a relationship between the dihedral angular dependence and the entanglement. We also found that the entangled excitations are related to electron correlation. The new formalism can be applied to all other response properties.