Multiple solvation configurations around phthalocyanine in helium droplets.
Recent measurements of the emission spectrum of phthalocyanine solvated in superfluid helium nanodroplets exhibit a constant 10.3 cm(-1) splitting of each emission line relative to the absorption spectrum. This splitting has been attributed to two distinct helium environments near the surface of the phthalocyanine molecule. Rigid-body path-integral Monte Carlo provides a means of investigating the origin of the splitting on a detailed microscopic level. Path-integral Monte Carlo simulations of 4He(N)-phthalocyanine at 0.625 K with N ranging from 24 to 150 show two distinct helium configurations. One configuration is commensurate with the molecular substrate and the other is a triangular lattice. We investigate the energetics of these two configurations and use a method for calculating electronic spectral shifts for aromatic molecule-rare-gas clusters due to dispersive interactions to estimate the spectral splitting that would arise from the two helium configurations seen for N=150. The results are in reasonable agreement with the experimentally measured splitting, supporting the existence of two distinct local helium environments near the surface of the molecule in the nanodroplets.
Whitley
Heather D
HD
Department of Chemistry and Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720, USA. hwhitley@berkeley.edu
Huang
Patrick
P
Kwon
Yongkyung
Y
Whaley
K Birgitta
KB