To ensure full coverage of the dynamically significant configuration space, it is important to perform sampling as comprehensively as possible. In this work, we focus solely on one isomerization channel. To initiate the sampling, we propose to use the Ab Initio Molecular Dynamics (AIMD) simulation near the MEP to ensure that the main feature of the PES is captured. Also, selecting the right method for AIMD is crucial, just as choosing the method for electronic structure calculations is. However, the CCSD(T)-F12a/AVTZ method for AIMD simulations is impractical due to its expensive cost. In this work, we carried out a comparative analysis of various relatively low-level methods using the ORCA software package, and the results are summarized in Table . The r2SCAN-3c method yields comparable outcomes with the CCSD(T)-f12a/AVTZ method while taking less time. Hence, we select the r2SCAN-3c method to run AIMD simulations for the initial sampling.