Rovibrational spectra for the HCCCN*HCN and HCN*HCCCN binary complexes in 4He droplets.
Rovibrational spectra are measured for the HCCCN*HCN and HCN*HCCCN binary complexes in helium droplets at low temperature. Though no Q-branch is observed in the infrared spectrum of the linear HCN*HCCCN dimer, which is consistent with previous experimental results obtained for other linear molecules, a prominent Q-branch is found in the corresponding infrared spectrum of the HCCCN*HCN complex. This Q-branch, which is reminiscent of the spectrum of a parallel band of a prolate symmetric top, implies that some component of the total angular momentum is parallel to the molecular axis. The appearance of this particular spectroscopic feature is analyzed here in terms of a nonsuperfluid helium density induced by the molecular interactions. Finite temperature path integral Monte Carlo simulations are performed using potential energy surfaces calculated with second-order Möller-Plesset perturbation theory, to investigate the structural and superfluid properties of both HCCCN*HCN(4He)N and HCN*HCCCN(4He)N clusters with N < or = 200. Explicit calculation of local and global nonsuperfluid densities demonstrates that this difference in the rovibrational spectra of the HCCCN*HCN and HCN*HCCCN binary complexes in helium can be accounted for by local differences in the superfluid response to rotations about the molecular axis, i.e., different parallel nonsuperfluid densities. The parallel and perpendicular nonsuperfluid densities are found to be correlated with the locations and strengths of extrema in the dimer interaction potentials with helium, differences between which derive from the variable extent of polarization of the CN bond in cyanoacetylene and the hydrogen-bonded CH unit in the two isomers. Calculation of the corresponding helium moments of inertia and effective rotational constants of the binary complexes yields overall good agreement with the experimental values.
Paesani
Francesco
F
Department of Chemistry and Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720, USA.
Whaley
K Birgitta
KB
Douberly
Gary E
GE
Miller
Roger E
RE
D002244:Carbon / Q000737:chemistry; D019281:Dimerization; D006371:Helium / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D006860:Hydrogen Bonding; D006856:Hydrogen Cyanide / Q000737:chemistry*; D046911:Macromolecular Substances / Q000737:chemistry; D009010:Monte Carlo Method; D049329:Nanostructures; D009570:Nitriles / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013696:Temperature
D046911:Macromolecular Substances; D009570:Nitriles; D006371:Helium; D006856:Hydrogen Cyanide; D002244:Carbon; D006859:Hydrogen; D009584:Nitrogen