Quantum dynamics of the vibrations of helium bound to the nanosurface of a large planar organic molecule: Phthalocyanine • he van der waals complex

We report rigorous quantum three-dimensional calculations of highly excited intermolecular vibrational states of the van der Waals (vdW) complex phthalocyanine• He (Pc• He). The Pc molecule was treated as rigid and the intermolecular potential energy surface (IPES) was represented as a sum of atom-atom Lennard-Jones pair potentials. The IPES has four equivalent global minima on the diagonals of the square-shaped Pc, inside its five-membered rings, and four slightly shallower local minima between them, creating a distinctive corrugation pattern of the molecular nanosurface. The vdW vibrational states analyzed in this work extend to about two-thirds of the well depth of the IPES. For the assignment of the in-plane (xy) vdW vibrational excitations it was necessary to resort to two sets of quantum numbers, the Cartesian quantum numbers [vx, vy] and the quantum numbers (v, l) of the 2D isotropic oscillator, depending on the nodal structure and the symmetry of the wave functions. The delocalization of the He atom parallel to the molecular surface is large already in the ground vdW state. It increases rapidly with the number of quanta in the in-plane vdW vibrations, with the maximum root-mean-square amplitudes Ax and Ay of about 7 au at the excitation energies around 40 cm-1. The wave functions of the highly excited states tend to be delocalized over the entire nanosurface and often have a square shape, reflecting that of the substrate.