In this paper, we propose two methods of calculating theoretically maximal metamer mismatch volumes. Unlike prior art techniques, our methods do not make any assumptions on the shape of spectra on the boundary of the mismatch volumes. Both methods utilize a spherical sampling approach, but they calculate mismatch volumes in two different ways. The first method uses a linear programming optimization, while the second is a computational geometry approach based on half-space intersection. We show that under certain conditions the theoretically maximal metamer mismatch volume is significantly larger than the one approximated using a prior art method.