期刊
JOURNAL OF CHEMICAL PHYSICS
卷 113, 期 23, 页码 10535-10550出版社
AMER INST PHYSICS
DOI: 10.1063/1.1324003
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High-resolution helium nanodroplet isolation spectra of the first overtone (2 nu (1)) of the acetylenic stretch of several substituted acetylenes (RC equivalent toC-H) at T=0.38 K, have been observed for the first time. A tunable 1.5 mum laser is coupled, using a power buildup cavity, to a beam of He droplets seeded with the molecule to be studied. Absorption spectra are recorded by monitoring the beam depletion as a function of laser frequency with a thermal detector. The spectra of hydrogen cyanide (HCN), monodeuteroacetylene (DCCH), cyanoacetylene (NCCCH), propyne (CH3CCH), trifluoropropyne (CF3CCH), 3,3-dimethylbutyne ((CH3)(3)CCCH), and trimethylsilylacetylene ((CH3)(3)SiCCH) have been recorded. Due to the superfluid nature of the droplet, rotational resolution is achieved despite the presence of some solvent-induced broadening. The spectroscopic constants have been extracted by means of spectral simulations. The resulting rotational constants are smaller than for the bare molecule by a factor which depends on the molecule nonsphericity and its gas-phase moment of inertia. The linewidths are found to be at least twice as large as those of the corresponding fundamental (nu (1)) transitions observed in a helium droplet by Nauta [Faraday Discuss. Chem. Soc. 113, 261 (1999) and references therein]. The helium-induced spectral shifts are found to be very small, but cannot be easily rationalized. (C) 2000 American Institute of Physics. [S0021-9606(00)00147-1].
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