Acetylene-furan trimer formation at 0.37 K as a model for ultracold aggregation of non- and weakly polar molecules

Abstract

We have studied the aggregation process of (C2H 2)⋯furan trimers at ultracold temperatures (0.37 K) in helium nanodroplets. Computational sampling of the potential energy surface using the multiple-minima-hypersurface (MMH) approach yielded seven possible minimum structures, optimized at the MP2 level of theory with the cc-pVTZ and 6-311++G(d,p) basis sets. Experimentally, we could assign five transitions in the IR spectrum of acetylene-furan aggregates in the acetylene C-H asym stretch region between 3240 and 3300 cm-1 to vibrational bands of the 2:1 acetylene-furan trimer. The transitions were assigned to three ring structures that all contain the T-shaped acetylene dimer as structural sub-motif. Two of the structures form a nonplanar ring involving a C-HAc⋯πFu bond, the third is a nearly planar ring containing a C-HAc⋯OFu bond. This assignment was corroborated by quantum mechanical/molecular dynamics (QM/MD) simulations mimicking in detail the aggregation process of precooled monomers. The simulations provided evidence for a transition from a higher level local minimum to the global minimum state over a small barrier during the aggregation process. The experimentally observed structures can be explained by a step-by-step aggregation of moieties pre-cooled to 0.37 K that are steered by intermediate and short-range electrostatic interactions. Thus, we are able to unravel a special aggregation mechanism which differs from aggregation of molecules with large dipole moments where this aggregation process is dominated by long range 1/r3 dipole-dipole interaction ("electrostatic steering"). This mechanism is expected to be a general mechanism in ultracold chemistry. Brrrr-cold! The aggregation process of (C2H 2)⋯furan trimers at ultracold temperatures (0.37 K) in helium nanodroplets is studied by a combination of computational and spectroscopic techniques. The results unravel a special aggregation mechanism for non- and weakly polar molecules, which is expected to be generally applicable in ultracold chemistry.