Some problems in applications of the linear variational method

The linear variational method is a standard computational method in quantum mechanics and quantum chemistry. As taught in most classes, the general guidance is to include as many basis functions as practical in the variational wave function. However, if it is desired to study the patterns of energy change accompanying the change of system parameters such as the shape and strength of the potential energy, the problem becomes more complicated. We use one-dimensional systems with a particle in a rectangular or in a harmonic potential confined in an infinite rectangular box to illustrate situations where a variational calculation can give incorrect results. These situations result when the energy of the lowest eigenvalue is strongly dependent on the parameters that describe the shape and strength of the potential. The numerical examples described in this work are provided as cautionary notes for practitioners of numerical variational calculations.