Can X-ray constrained Hartree-Fock wavefunctions retrieve electron correlation?

Abstract

The X-ray constrained wavefunction (XC-WF) method proposed by Jayatilaka [Jayatilaka & Grimwood (2001) ▸, Acta Cryst. A57, 76-86] has attracted much attention because it represents a possible third way of theoretically studying the electronic structure of atoms and molecules, combining features of the more popular wavefunction- and DFT-based approaches. In its original formulation, the XC-WF technique extracts statistically plausible wavefunctions from experimental X-ray diffraction data of molecular crystals. A weight is used to constrain the pure Hartree-Fock solution to the observed X-ray structure factors. Despite the wavefunction being a single Slater determinant, it is generally assumed that its flexibility could guarantee the capture, better than any other experimental model, of electron correlation effects, absent in the Hartree-Fock Hamiltonian but present in the structure factors measured experimentally. However, although the approach has been known for long time, careful testing of this fundamental hypothesis is still missing. Since a formal demonstration is impossible, the validation can only be done heuristically and, to accomplish this task, X-ray constrained Hartree-Fock calculations have been performed using structure factor amplitudes computed at a very high correlation level (coupled cluster) for selected molecules in isolation, in order to avoid the perturbations due to intermolecular interactions. The results show that a single-determinant XC-WF is able to capture the electron correlation effects only partially. The largest amount of electron correlation is extracted when: (i) a large external weight is used (much larger than what has normally been used in XC-WF calculations using experimental data); and (ii) the high-order reflections, which carry less information on the electron correlation, are down-weighted (or even excluded), otherwise they would bias the fitting towards the unconstrained Hartree-Fock wavefunction.