Spin-rotation and NMR shielding constants in HCl
- Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Kasprzaka 44 (Poland)
- Centre for Theoretical and Computational Chemistry, University of Tromsø—The Arctic University of Norway, N-9037 Tromsø (Norway)
- Laboratory of NMR Spectroscopy, Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)
The spin-rotation and nuclear magnetic shielding constants are analysed for both nuclei in the HCl molecule. Nonrelativistic ab initio calculations at the CCSD(T) level of approximation show that it is essential to include relativistic effects to obtain spin-rotation constants consistent with accurate experimental data. Our best estimates for the spin-rotation constants of {sup 1}H{sup 35}Cl are C{sub Cl} = −53.914 kHz and C{sub H} = 42.672 kHz (for the lowest rovibrational level). For the chlorine shielding constant, the ab initio value computed including the relativistic corrections, σ(Cl) = 976.202 ppm, provides a new absolute shielding scale; for hydrogen we find σ(H) = 31.403 ppm (both at 300 K). Combining the theoretical results with our new gas-phase NMR experimental data allows us to improve the accuracy of the magnetic dipole moments of both chlorine isotopes. For the hydrogen shielding constant, including relativistic effects yields better agreement between experimental and computed values.
- OSTI ID:
- 22253761
- Journal Information:
- Journal of Chemical Physics, Vol. 139, Issue 23; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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