Quantum Statistical Corrections to Dynamic Nuclear Magnetic Resonance
作者： Leonard J Mueller , Daniel P Weitekamp
DOI: 10.1126/SCIENCE.283.5398.61
关键词: Equilibrium constant 、 Operator (physics) 、 Vibrational energy relaxation 、 Interpretation (model theory) 、 Methylcyclohexane 、 Nuclear magnetic resonance 、 Range (particle radiation) 、 Quantum 、 Eigenvalues and eigenvectors 、 Chemistry
摘要: A quantum statistical treatment of the chemical exchange between molecular eigenstates or conformations revealed previously unsuspected dynamic terms in spin Hamiltonian operator that describes fast exchange. These resulted from effect nuclear on rotational and vibrational relaxation. With traditional theory, an interpretation new carbon-13 magnetic resonance measurements shift methylcyclohexane solution showed fast-exchange equilibrium constants were inconsistent with slow-exchange free-energy difference spread over a range 30 percent for various positions. Modeling indicated they have correct magnitude temperature dependence to reconcile these inconsistencies.
sciencemag.org
unirioja.es
core.ac.uk
harvard.edu参考文章(13)
S. Szymański, M. Witanowski, A. Gryff-Keller, Problems in Theory and Analysis of Dynamic Nuclear Magnetic Resonance Spectra Annual reports on NMR spectroscopy. ,vol. 8, pp. 227- 289 ,(1978) , 10.1016/S0066-4103(08)60300-2
H. S. Gutowsky, D. W. McCall, C. P. Slichter, Nuclear Magnetic Resonance Multiplets in Liquids The Journal of Chemical Physics. ,vol. 21, pp. 279- 292 ,(1953) , 10.1063/1.1698874
D.M Doddrell, D.T Pegg, M.R Bendall, Distortionless enhancement of NMR signals by polarization transfer Journal of Magnetic Resonance. ,vol. 48, pp. 323- 327 ,(1982) , 10.1016/0022-2364(82)90286-4
Eric R. Johnston, Jodi S. Barber, Marc Jacomet, James C. Barborak, NMR MOTIONAL AVERAGING IN THE ISOTOPICALLY PERTURBED COPE REARRANGEMENT Journal of the American Chemical Society. ,vol. 120, pp. 1489- 1493 ,(1998) , 10.1021/JA970281J
Lawrence G. Werbelow, NMR dynamic frequency shifts and the quadrupolar interaction Journal of Chemical Physics. ,vol. 70, pp. 5381- 5383 ,(1979) , 10.1063/1.437471
Frank A.L. Anet, Darón I. Freedberg, Traditional averaging of NMR parameters in the fast exchange limit is valid Chemical Physics Letters. ,vol. 208, pp. 187- 192 ,(1993) , 10.1016/0009-2614(93)89059-Q
K.E. Ohara, C.P. Slichter, Reexamination of Motional Averaging in Magnetic Resonance Journal of Magnetic Resonance, Series A. ,vol. 109, pp. 74- 79 ,(1994) , 10.1006/JMRA.1994.1136
Alexander J Vega, Daniel Fiat, Relaxation theory and the stochastic Liouville equation Journal of Magnetic Resonance. ,vol. 19, pp. 21- 30 ,(1975) , 10.1016/0022-2364(75)90024-4
Anthony L. Van Geet, Calibration of methanol nuclear magnetic resonance thermometer at low temperature Analytical Chemistry. ,vol. 42, pp. 679- 680 ,(1970) , 10.1021/AC60288A022
Michael E. Squillacote, Joann M. Neth, Complete 13C NMR spectra of the axial forms of methyl-, ethyl- and isopropylcyclohexane Magnetic Resonance in Chemistry. ,vol. 25, pp. 53- 56 ,(1987) , 10.1002/MRC.1260250113