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clustering and concomitant appearance of multiple cluster spectral features.
Fast spin inter-conversion impedes our ability to form water clusters entirely from
p-H2O molecules. Panels (a) – (e) in Fig. 7.5 demonstrate the stages of clustering
observed upon completion of ~ 40 min 1:1000 H2O:Ar sample deposition at 4 K (a) with
an OPR of about 1.5:1, ~ 1730 min conversion at 4 K (b), annealing to 30 K for 1 min
(c), continued annealing at T = 30 K for 5 min (d), and re-cooling back to 4 K (e). Upon
immediate heating to 30 K, as observed in panel (c), the 000 → 101 para transition at 3756
cm-1 is dominant despite the onset of clustering. Thus we have concluded that small
clusters are formed from predominantly p-H2O molecules. In addition, we observed the
growth of 111 → 110 (para) and 110 → 111 (ortho) transitions at 3738.8 and 3725.0 cm-1,
respectively, as observed previously.12 Upon continued annealing at T = 30 K for ~ 5 min
(d), intensity growth of ortho and subsequent decrease of para transitions are observed.
Re-cooling the sample to T = 4 K shows the return of 000 ← 101 and 202 ← 101 lines with
OPR of about 1:1. In addition, the para AA band of the water dimer is observed at
3736.4 cm-1 as will be discussed below.
166
Object Description
| Title | Infrared and Raman spectrosopy of molecules and molecular aggregates in helium droplets |
| Author | Sliter, Russell Thomas |
| Author email | sliter@usc.edu; sliterr@gmail.com |
| Degree | Doctor of Philosophy |
| Document type | Dissertation |
| Degree program | Chemistry |
| School | College of Letters, Arts and Sciences |
| Date defended/completed | 2011-04-21 |
| Date submitted | 2011 |
| Restricted until | Unrestricted |
| Date published | 2011-04-26 |
| Advisor (committee chair) | Vilesov, Andrey F. |
| Advisor (committee member) |
Reisler, Hannah Kresin, Vitaly V. |
| Abstract | This dissertation covers several different aspects of spectroscopy of molecules and molecular clusters embedded in low-temperature matrices, such as helium droplets. First, details on the formation and optimization of He droplets will be discussed. A new method of measuring droplet sizes for cw nozzle expansions using mass spectrometry was developed. The results of the measurements of the sizes of the droplets in pulsed expansion as a function of temperature will be described. Details on the electron-impact ionization of He droplets will also be discussed as well as a simple method of modeling the ionization and excitation of He atoms in the droplet. In addition, preliminary measurements on the size distribution of He droplets produced at very low temperature of 5 – 7 K in continuous expansion will be addressed.; Using matrix isolation in He droplets, vibrational spectra of clusters consisting of para-H₂ or para-H₂/D₂ have been obtained using coherent anti-Stokes Raman spectroscopy (CARS). The vibrational frequency of para-H₂ molecules obtained upon expansion of neat para-H₂/D₂ gas or liquid was found to be very similar to that in bulk solid samples having equal composition. On the other hand, spectra in clusters obtained upon expansion of 1% para-H₂/D₂ clusters seeded in He are liquid and have a considerable frequency shift, which indicate phase separation of the two isotopes in clusters at low temperature. The onset of phase separation in para-H₂/D₂ mixtures is predicted at approximately 3 K providing further evidence of super-cooled liquid hydrogen clusters.; To address the Raman spectra observed in liquid H2 clusters, vibrational and rotational spectra of bulk liquid para-H2 at temperature of T = 14 – 26 K and of solid at T = 6 – 13 K have been obtained using coherent anti-Stokes Raman scattering technique. The vibrational frequency in the liquid increases with temperature by about 2 cm⁻¹, and the shift scales with the square of the sample’s density. An extrapolation of the vibrational frequency in the metastable para-H₂ liquid below the freezing point is discussed. The results indicate that the vibron hopping between the molecules is active in the liquid, similar to that previously found in the solid.; Matrix isolation has also been performed in argon solid matrices based on a custom-made cryogenic optical cell. Single water molecules have been isolated in solid Ar matrices at 4 K and studied by ro-vibrational spectroscopy using FTIR in the regions of the v₁, v₂, and v₃ modes. Upon nuclear spin conversion at 4 K, essentially pure para-H₂O was prepared followed by subsequent fast annealing generating ice particles. FTIR studies of the vapor above the condensed water upon annealing to T ≥ 250 K indicate fast re-conversion of nuclear spin to equilibrium conditions. Our results indicate that nuclear spin conversion is fast in water dimers and larger clusters, which preclude preparation of concentrated samples of para-H₂O, such as in ice or vapor. |
| Keyword | Helium droplets; laser spectroscopy; matrix isolation; superfluidity; clusters |
| Language | English |
| Part of collection | University of Southern California dissertations and theses |
| Publisher (of the original version) | University of Southern California |
| Place of publication (of the original version) | Los Angeles, California |
| Publisher (of the digital version) | University of Southern California. Libraries |
| Provenance | Electronically uploaded by the author |
| Type | texts |
| Legacy record ID | usctheses-m3778 |
| Contributing entity | University of Southern California |
| Rights | Sliter, Russell Thomas |
| Repository name | Libraries, University of Southern California |
| Repository address | Los Angeles, California |
| Repository email | cisadmin@lib.usc.edu |
| Filename | etd-Sliter-4404 |
| Archival file | uscthesesreloadpub_Volume23/etd-Sliter-4404.pdf |
Description
| Title | Page 190 |
| Contributing entity | University of Southern California |
| Repository email | cisadmin@lib.usc.edu |
| Full text | clustering and concomitant appearance of multiple cluster spectral features. Fast spin inter-conversion impedes our ability to form water clusters entirely from p-H2O molecules. Panels (a) – (e) in Fig. 7.5 demonstrate the stages of clustering observed upon completion of ~ 40 min 1:1000 H2O:Ar sample deposition at 4 K (a) with an OPR of about 1.5:1, ~ 1730 min conversion at 4 K (b), annealing to 30 K for 1 min (c), continued annealing at T = 30 K for 5 min (d), and re-cooling back to 4 K (e). Upon immediate heating to 30 K, as observed in panel (c), the 000 → 101 para transition at 3756 cm-1 is dominant despite the onset of clustering. Thus we have concluded that small clusters are formed from predominantly p-H2O molecules. In addition, we observed the growth of 111 → 110 (para) and 110 → 111 (ortho) transitions at 3738.8 and 3725.0 cm-1, respectively, as observed previously.12 Upon continued annealing at T = 30 K for ~ 5 min (d), intensity growth of ortho and subsequent decrease of para transitions are observed. Re-cooling the sample to T = 4 K shows the return of 000 ← 101 and 202 ← 101 lines with OPR of about 1:1. In addition, the para AA band of the water dimer is observed at 3736.4 cm-1 as will be discussed below. 166 |
