An explicitly correlated potential energy surface for N2–OCS complex: Out-of-plane motion and tunneling dynamics

A four-dimensional potential energy surface (4D-PES) has been constructed for the N2-OCS complex. The PES is achieved by applying the explicitly correlated coupled cluster method, which incorporates single, double, and perturbative triple excitations [CCSD(T)-F12a], along with the augmented correlation consistent triple zeta (aug-cc-pVTZ) basis set. The rovibrational levels are precisely determined and assigned through bound state calculations and wavefunction analysis. The calculated transition frequencies reproduce the experimental observations accurately, achieving an RMSE of 0.0005 cm-1 for the 23 rotational transitions (J ≤ 6, Ka ≤ 2). The R-φ contour plot of the wave function clearly demonstrates the unambiguous delocalization of the dihedral angle, and the averaged geometry of the ground vibrational state is determined to be non-planar with φ = 90°. To obtain a quantitative analysis of this phenomenon, we expanded the 3H-solution model [Guo et al., J. Quant. Spectrosc. Radiat. Transfer 309 (2023) 108711] from a three-dimensional system (Ar-AgF) to a nine-dimensional system (N2-OCS). Based on this model, the tunneling splitting was calculated to be 0.0822 cm-1, which excellently matches the experimental result of 0.0817 cm-1. The excellent agreement between the theoretical and experimental results suggests that the wavefunction delocalization and out-of-plane motion can be attributed to the tunneling effects in the ground vibrational state.