Spin-rotation and NMR shielding constants in HCl
| Autor: | Michal Repisky, Elena Malkin, Michał Jaszuński, Piotr Garbacz, Kenneth Ruud, Stanislav Komorovsky, Karol Jackowski, Taye B. Demissie, Włodzimierz Makulski |
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| Rok vydání: | 2013 |
| Předmět: |
Magnetic moment
Chemistry Isotopes of chlorine Ab initio General Physics and Astronomy Rotational–vibrational spectroscopy VDP::Matematikk og Naturvitenskap: 400::Kjemi: 440::Fysikalsk kjemi: 443 Ab initio quantum chemistry methods Electromagnetic shielding Kinetic isotope effect Physics::Atomic Physics Physical and Theoretical Chemistry Atomic physics Physics::Chemical Physics VDP::Mathematics and natural science: 400::Chemistry: 440::Physical chemistry: 443 Relativistic quantum chemistry |
| Zdroj: | The Journal of chemical physics. 139(23) |
| ISSN: | 1089-7690 |
| Popis: | 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 (1)H(35)Cl are CCl = -53.914 kHz and C(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. |
| Databáze: | OpenAIRE |
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