Bridging the Gap between Small Clusters and Nanodroplets: Spectroscopic Study and Computer Simulation of Carbon Dioxide Solvated with Helium Atoms

Abstract

High resolution infrared spectra of He(N)-CO2 clusters with N up to 17 have been studied in the region of the CO2 nu(3) fundamental band. The B rotational constant initially drops as expected for a normal molecule, reaching a minimum for N=5. Its subsequent rise for N=6 to 11 can be interpreted as the transition from a normal (though floppy) molecule to a quantum solvation regime. For N>13, the B value becomes approximately constant with a value about 17% larger than that measured in much larger helium nanodroplets. Quantum Monte Carlo calculations of pure rotational spectra are in excellent agreement with the measured B in this size range and complement the experimental study with detailed structural information. For a larger cluster size (N=30-50) the simulations show a clear sign of convergence towards the nanodroplet B value.