The primary dielectric relaxation process of monoalcohols typically exhibits characteristic Debye behavior, and the factors influencing its rate have become a research focus in recent years. It is generally believed that the hydrophilic end (i.e., the hydroxyl group) of alcohol molecules plays a major role in the primary dielectric relaxation process through hydrogen bonding networks, while the hydrophobic end mainly exerts an indirect effect by influencing the formation of intermolecular hydrogen bonds. This study systematically investigates the factors influencing the primary dielectric relaxation process of methanol using molecular dynamics simulations. As the simplest alcohol molecule, studying methanol can provide insights into the common characteristics of monohydroxy alcohols and even alcohols in general. The well-known "wait-and-switch" model currently emphasizes the impact of hydrogen bond partner concentration on the primary dielectric relaxation rate of the system. In this study, we systematically investigated the factors influencing the primary dielectric relaxation rate of methanol by independently adjusting the O-H bond length (
doh), the C-O bond length (
doc), and the methyl diameter (
σmethyl) of methanol molecules, and provided significant extensions to the "wait-and-switch" model:1) By adjusting
doh, we found that a stronger total hydrogen bond energy (
UHB) in the system enhances the correlation of molecular motion, slowing down the reorientation rate of molecules and, consequently, the primary dielectric relaxation process of the system. 2) By adjusting
dco, we discovered that a longer hydrophobic end not only slows down the primary dielectric relaxation process by stabilizing the intermolecular hydrogen bond network but also directly reduces the rate of this process. 3) By adjusting
σmethyl, we found that an excessively small
σmethylis detrimental to the stability of the hydrogen bond network, while an excessively large
σmethylhinders the formation of hydrogen bonds. Both cases negatively affect the correlation of molecular motion. The primary dielectric relaxation process of the system is slowest when
σmethylis at a moderate level. It was ultimately found that factors such as
UHBand the volume of the correlated motion (
VCM), along with the concentration of hydrogen bond partners in the system, collectively form the key elements influencing the primary dielectric relaxation rate of the system. Our results can reasonably explain experimental phenomena that the original "wait-and-switch" model could not account for. This study contributes to a deeper understanding of the relaxation processes of alcohol molecules and their physical origins.