Towards the generation of potential energy surfaces of weakly bound medium-sized molecular systems: the case of benzonitrile-He complex

Currently, the explicitly correlated coupled cluster method is used routinely to generate the multi-dimensional potential energy surfaces (mD-PESs) of van der Waals complexes of small molecular systems relevant for atmospheric, astrophysical and industrial applications. Although very accurate, this method is computationally prohibitive for medium and large molecules containing clusters. For instance, the recent detections of complex organic molecules (COMs) in the interstellar medium, such as benzonitrile, revealed the need to establish an accurate enough electronic structure approach to map the mD-PESs of these species interacting with the surrounding gases. As a benchmark, we have treated the case of the polar molecule benzonitrile interacting with helium, where we use post-Hartree-Fock and symmetry-adapted perturbation theory (SAPT) techniques. Accordingly, we show that MP2 and distinguishable-cluster approximation (DCSD) cannot be used for this purpose, whereas accurate enough PESs may be obtained using the corresponding explicitly correlated versions (MP2-F12 or DCSD-F12) with a reduction in computational costs. Alternatively, computations revealed that SAPT(DFT) is as performant as CCSD(T)-F12/aug-cc-pVTZ, making it the method of choice for mapping the mD-PESs of COMs containing clusters. Therefore, we have used this approach to generate the 3D-PES of the benzonitrile-He complex along the intermonomer Jacobi coordinates. As an application, we have incorporated the analytic form of this PES into quantum dynamical computations to determine the cross sections of the rotational (de-)excitation of benzonitrile colliding with helium at a collision energy of 10 cm-1. We establish an accurate methodology for the generation of mD-PESs of medium sized and large molecules containing van der Waals complexes. We discuss the case of benzonitrile-He as benchmark system.