We theoretically study here the homolytic dissociation reactions of sterically crowded alkanes of increasing size, carrying three different (bulky) substituents such as tert-butyl, adamantyl, and [1.1.1]propellanyl, employing a family of parameter-free functionals ranging from semi-local, to hybrid and double-hybrid models. The study is complemented with the interaction between a pair of HC(CH3)3 molecules at repulsive and attractive regions, as an example of a system composed by a pair of weakly bound sterically crowded alkanes. We also assessed the effect of incorporating reliable dispersion corrections (i. e., D4 or NL) for all the functionals assessed, as well as the use of a tailored basis set (DH-SVPD) for non-covalent interactions, which provides the best trade-off between accuracy and computational cost for a seemingly extended applications to branched or crowded systems. Overall, the PBE-QIDH/DH-SVPD and r2SCAN-QIDH/DH-SVPD methods represent an excellent compromise providing relatively low, and thus very competitive, errors at a fraction of the cost of other quantum-chemical methods in use.