In the last two decades, linear-response time-dependent density functional theory (LR-TDDFT) has become one of the most widely used approaches for the computation of the excited-state properties of atoms and molecules. Despite its success in describing the photochemistry and the photophysics of a vast majority of molecular systems, its domain of applicability has been limited by several substantial drawbacks. Commonly identified problems of LR-TDDFT include the correct description of Rydberg states, charge-transfer excited states, doubly excited states, and nearly degenerate states. In addition to these widely recognized shortcomings, the approximate functionals used in LR-TDDFT are unable to fully describe London dispersion interactions. In this work, we aim at understanding the impact of van der Waals interactions on the properties of chemical systems beyond their electronic ground state. For this purpose, we compare the results of excited-state energy profiles and dynamic trajectories for the prototypical cis-stilbene molecule with its 3-3′,5-5′-tetra-tert-butyl derivative. While the explicit treatment of London dispersion interactions results in negligible changes for the cis-stilbene, we show that these attractive forces have a substantial influence on the energetics and structural evolution of the substituted derivative. In the latter case, intramolecular dispersion interactions impact the outcome of the simulation qualitatively, leading to an increased preference for the photocyclization pathway. The methodological consequences of this work are not uniquely applicable to the illustrative stilbene case. In fact, this molecule is representative of a whole class of chemical situations, where dispersion forces dominate the interactions between the unexcited substituents of a photoexcited chromophore. This is, for instance, a common situation in organic photovoltaics where donor molecules are usually functionalized with long alkyl side chains to improve solubility and assembly.