Orthogonal effect of exchange and correlation parameters in density functional theory to compute geometric and spectroscopic quantities

The influence of the composition of the functional used for density functional theory computations on one structural parameter (a dihedral angle) and a spectroscopic parameter (absorption wavelength) is assessed in this study on the basis of two molecules (flavonols). In this kind of molecules, these two parameters should be correlated according to the nature of the electronic transition involved. However, it is shown herein that by varying the proportion of true exchange and correlation while building a functional, it is possible to obtain independently a large range of values for these parameters without any relation with the underlying real values. Therefore, it is concluded that the choice of a functional after a benchmark, especially using user‐defined functionals, should be carried out with great care to avoid such effects. The reproduction of the ultraviolet spectrum of a molecule by the means of time‐dependent density functional theory is naturally linked to the choice of a good functional, but this choice has consequences on the reproduction of other quantities, a dihedral angle in this study. This structural effect should not be overlooked as the behavior is, in some cases, quite unpredictable and unrelated to the quality of the ultraviolet spectrum reproduction.