The vibrational, rotational, and translational motions at the initial reactant asymptote can be sampled according to the Boltzmann distribution at some specified temperature, for instance, 3000 K, which is sufficiently high to access all dynamically relevant regions. Thermal kinetics often require the temperature as high as 3000 K, particularly for combustion. In most cases, the resulting sampling is appropriate. The research target is related to the sampling. If only reactivity initialized from the ground ro-vibrational reactants is focused at different collision energies, the sampling range is generally narrower than that by the thermal sampling of each degree of freedom at 3000 K. If only the forward reaction is focused, the configurations in the product channels may be not well sampled and the corresponding PES is generally not appropriate for the reverse. For ro-vibrational spectra of the simplest Criegee intermediate, CH2OO, and its isomer, dioxirane, 117 only configurations around CH2OO and dioxirane are needed. No configuration for the reactive channel such as H2CO + O and HCO + OH is required. Similarly, for the ro-vibrational spectra of the weakly interacted complexes, such as H2O…HCl 118-120 and H2O…CO, sampling for other regions except the wells is not helpful for the research target. For low-temperature or low-energy kinetics or dynamics, long-range regions between reactants or products need be well sampled for long-range interactions. For the H2 + HCl inelastic scattering, a total of 42417 points were selected to cover regions with the center-of-mass distance between H2 and HCl up to 30 Å. For the ion-molecule reaction, H2 + NH2 -↔ H -+ NH3, the sampling points cover a very large dynamical relevant configuration space. As shown in Figure , there still exists weak interactions, even the distance between NH2 -and H2 or between NH3 and H - reaches 50 Å. Hence, 98 154 points were sampled in a large configuration space to provide reliable descriptions for both long-range and strong-interacted regions. For efficiency and accuracy, it is often to represent the long-range interaction in the multipolar expansion form. For gases in shock tubes, shocked gases surrounding hypersonic Earth-re-entry vehicles, the chemical species may be highly excited in the ro-vibrational and translational degrees of freedom, resulting far-from-equilibrium energy populations. During hypersonic flight through Earth's atmosphere, the translational temperature of the air (most are N2 and O2) in front of the vehicle can reach 10000 K and the internal vibrational energy can be close to the dissociation threshold. Therefore, the sampling configurations for N2 + N2 and N2 + O2 cover fully dissociated regions for N +N + N + N or N + N + O + O, and the energies of the sampling points span up to 2000 kcal/mol. For the plasma chemistry, such as CO (v) + CO (v′) 132 or CO2 (v) + CO2 (v′), 133 high internal vibrational excitations and low collision energies would sample the corresponding configurations.