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https://hdl.handle.net/2440/87667
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Type: | Journal article |
Title: | Rotational study of carbon monoxide isotopologues in small ⁴He clusters |
Other Titles: | Rotational study of carbon monoxide isotopologues in small (4)He clusters |
Author: | Raston, P. Xu, Y. Jager, W. Potapov, A. Surin, L. Dumesh, B. Schlemmer, S. |
Citation: | Physical Chemistry Chemical Physics, 2010; 12(29):8260-8267 |
Publisher: | Royal Society of Chemistry |
Issue Date: | 2010 |
ISSN: | 1463-9076 1463-9084 |
Statement of Responsibility: | P. L. Raston, Y. Xu, W. Jäger, A. V. Potapov, L. A. Surin, B. S. Dumesh and S. Schlemmer |
Abstract: | High resolution microwave (a-type) and millimetre-wave (b-type) spectra of HeN–13C16O, HeN–12C18O, and HeN–13C18O clusters (N ≤ 10) were observed, significantly extending the initial spectroscopic observations on HeN–12C16O by Surin et al. [Phys. Rev. Lett., 2008, 101, 233401]. The frequencies of the a-type series, which evolves from the end-over-end rotation of the dimer, decrease from N = 1 to 3, then increase smoothly to at least N = 9. This turnaround indicates a rapid evolution of the solvation character from classical to quantum. The b-type series, which evolves from the free molecule rotation of CO, increases from N = 0 to 6 and then decreases to at least N = 10. This is consistent with an initially increasing anisotropy of the helium environment, followed by a tendency of the solvation shell to become more isotropic. The shift of the vibrational frequency of CO as determined from the infrared [A. R. W. McKellar, J. Chem. Phys., 2004, 121, 6868; ibid., 2006, 125, 164328] and microwave data reveals an approximately linear decrease from N = 1 to at least 9. If the linear shift were to continue until completion of the first solvation shell (N ≈ 14), the estimated helium nanodroplet shift will be well undershot [K. von Haeften, S. Rudolph, I. Simanovski, M. Havenith, R. E. Zillich and K. B. Whaley, Phys. Rev. B: Condens. Matter Mater. Phys., 2006, 73, 054502]. In this case, there must be an upturn in the vibrational shift beyond N = 14, which is not predicted by theory [T. Škrbić, S. Moroni and S. Baroni, J. Phys. Chem. A, 2007, 111, 7640]. By extrapolating the a-type series to N = 14 (assuming a linear vibrational shift), we estimate the rotational constant, B, of CO in the helium nanodroplet to be [similar]74% of its gas phase value. This is in reasonable agreement with simulations (76% at N = 14), which predict the limiting value to be approximately reached upon completion of the first solvation shell (73% at N = 100) [T. Škrbić, S. Moroni and S. Baroni, J. Phys. Chem. A, 2007, 111, 7640]. However, this value is significantly larger than that inferred from helium nanodroplet experiments (63%). |
Rights: | Copyright status unknown |
DOI: | 10.1039/C0CP00193G |
Published version: | http://dx.doi.org/10.1039/c0cp00193g |
Appears in Collections: | Aurora harvest 7 Physics publications |
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