The effect of temperature is often neglected in computational studies that evaluate Al chemical shift, because ensemble averaging is computationally much more expensive than the local optimization approach (see Section 3.2) that is typically used. Herein the dependence of the Al chemical shift on the temperature was evaluated for the T5 position at the intersection by considering a temperature range from 250 K to 500 K with a step of 50 K. All possible BAS were modeled and subjected to MD simulations at different temperatures with varying water loading. The results are presented in Fig. , which depicts the change of the chemical shifts with temperature. For the dehydrated MFI model, the chemical shift remains nearly constant until a significant increase of about 1 ppm is observed between 350 K and 400 K. This sudden increase can be explained by the interaction of the BAS proton with the surrounding framework. At lower temperatures, the proton forms a hydrogen bond with another framework atom, i.e., an intrazeolitic hydrogen bond (IZB), leading to significant distortion of the aluminium environment. As the temperature rises, thermal motion reduces the contribution of the intrazeolitic hydrogen bonding mode in the structural ensemble (see Fig. in ESI †), i.e., the IZB is partially broken, as was also observed in some previous works. This reduction in intrazeolitic hydrogen bonding directly correlates with the observed jump in chemical shift, reflecting changes in the aluminium environment.