Stimulated Raman probing of supercooling and phase transitions in large N2 clusters formed in free jet expansions
- 15 June 1990
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 92 (12), 7068-7078
- https://doi.org/10.1063/1.458247
Abstract
High resolution stimulated Raman spectroscopy(SRS) has been used to examine N2 and N2/He free jet expansions and also equilibrium samples of N2 from 15 to 110 K. The jet spectra show the formation of large liquid clusters which supercool and subsequently freeze to form crystalline β‐N2solid and, in He expansions, undergo a further transformation to a partially annealed α‐N2 form. CW‐SRS frequency and linewidth data obtained for equilibrium samples of the condensed phases of N2 yielded frequency–temperature relations used in deducing internal temperatures for the clusters produced in the expansion experiments. Analysis of the cooling curves indicates a mean cluster diameter of 35 nm and favors a prompt freezing process rather than a gradual conversion of liquid to solid in a single cluster on the microsecond time scale of the experiments. Supercooling limits of 34 to 44 K are deduced for the liquid, far below the triple point temperature of 63.2 K at which equilibrium samples freeze. Some evidence for surface versus bulk contributions to the spectra is seen in the asymmetric line shapes observed for liquid clusters in the condensation region. The results show that the high spectral and spatial resolution of nonlinear Raman methods such as SRS and CARS provide a unique probe of the condensation processes in free jet expansions.Keywords
This publication has 27 references indexed in Scilit:
- Phases and phase changes of molecular clusters generated in supersonic flowThe Journal of Physical Chemistry, 1989
- Electron diffraction and Monte Carlo studies of liquids. 3. Supercooled benzeneJournal of the American Chemical Society, 1988
- Infrared spectroscopy of carbon dioxide ultrafine particlesThe Journal of Physical Chemistry, 1988
- Homogeneous condensation in nitrogen, argon, and water vapor free jetsThe Journal of Physical Chemistry, 1987
- Ionic clustersChemical Reviews, 1986
- Diffraction studies of clusters generated in supersonic flowChemical Reviews, 1986
- Infrared spectroscopy at the surface of clusters: SF6 on ArThe Journal of Chemical Physics, 1985
- Raman studies of argon dimers in a supersonic expansion. I. SpectroscopyPhysical Review A, 1983
- Scattered electron counting system for nozzle beam studies of small clustersReview of Scientific Instruments, 1982
- Densities of saturated liquid oxygen and nitrogenPhysica, 1969