Van der Waals Bonding to a Molecule with π-Electron Conjugation: Styrene-Argon Complex Studied by Mass Selective High Resolution R2PI UV Spectroscopy and Ab-initio Calculations

Abstract

Combining high-resolution mass-selective resonance-enhanced two-photon ionization spectroscopy analysed by genetic-algorithm-based computer-assisted rotational fit and high-level ab initio calculations we were able to determine the structure and the transition moment orientation of the styrene-Ar complex. The results demonstrate that Ar binds to the benzene ring of styrene. The binding site of Ar is 3.42 Å above the benzene-ring plane and is close to the C 6 symmetry axis of the aromatic ring, but slightly shifted to the vinyl group, which implies that the binding pattern is perturbed by the presence of the bonded to the benzene ring vinyl group. The transition moment ratio of the styrene-Ar complex is considerably different from the one of bare styrene this being a purely mass effect stemming from the reorientation of the principal axes of inertia upon the cluster formation. The red shift of the 00 0 origin band of the styrene-Ar2 complex is almost twice that of the single complex, indicating that the red-shift additivity rule holds in this case. On this basis we conclude that the second Ar atom is bound to the opposite side of the benzene ring.