On the termination of the X-ray constrained wavefunction procedure: reformulation of the method for an unequivocal determination of λ

Abstract

The X-ray constrained/restrained wavefunction (XCW/XRW) approach of quantum crystallography is revisited by introducing the stationary condition of the Jayatilaka functional with respect to the Lagrange multiplier λ. The theoretical derivation has unequivocally shown that the right value of λ is a maximum stationary point of the functional to optimize, thus enabling the solution of the longstanding problem of establishing the point at which to halt the XCW/XRW procedure. Based on the new finding, a reformulation of the X-ray constrained wavefunction algorithm is proposed and its implementation is envisaged. In addition to relying on more solid mathematical grounds, the new variant of the method will be intrinsically more physically meaningful, allowing a straightforward evaluation of the highest level of confidence with which the experimental X-ray diffraction data can be possibly reproduced.