Quantum statistical corrections to dynamic nuclear magnetic resonance

Science

Volumn 283, Issue 5398, 1999, Pages 61-65

  Mueller, Leonard J ^a   Weitekamp, Daniel P ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC HYDROCARBONS; CARBON; CHEMICAL RELAXATION; CONFORMATIONS; FREE ENERGY; IONIZATION; MATHEMATICAL TECHNIQUES; MOLECULAR VIBRATIONS; NUCLEAR MAGNETIC RESONANCE; STATISTICAL MECHANICS; THERMAL EFFECTS;

CHEMICAL EXCHANGE; EQUILIBRIUM CONSTANTS; METHYLCYCLOHEXANE; MOLECULAR EIGENSTATES; NUCLEAR SPIN; SPIN HAMILTONIAN;

QUANTUM THEORY;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CONFORMATIONAL TRANSITION; MOLECULAR DYNAMICS; PRIORITY JOURNAL; PROTON NUCLEAR MAGNETIC RESONANCE; THERMODYNAMICS;

EID: 0032902348     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.283.5398.61     Document Type: Article

References (35)

1. N. Bloembergen, E. M. Purcell, R. V. Pound, Phys. Rev. 73, 679 (1948).
2. E. L. Hahn and D. E. Maxwell, ibid. 88, 1070 (1952); H. S. Gutowsky, D. W. McCall, C. P. Slichter, J. Chem. Phys. 21, 279 (1953); H. M. McConnell, ibid. 28, 430 (1957); S. Alexander, ibid. 37, 967 (1962); C. S. Johnson, ibid. 41, 3277 (1964); R. M. Lynden-Bell, Prog. Nucl. Magn. Reson. Spectrosc. 2, 163 (1967); A. J. Vega and D. Fiat, J. Magn. Reson. 19, 21 (1974); S. Szymanski, M. Witanowski, A. Gryff-Keller, Annu. Rep. NMR Spectrosc. 8, 227 (1978).
3. E. L. Hahn and D. E. Maxwell, ibid. 88, 1070 (1952); H. S. Gutowsky, D. W. McCall, C. P. Slichter, J. Chem. Phys. 21, 279 (1953); H. M. McConnell, ibid. 28, 430 (1957); S. Alexander, ibid. 37, 967 (1962); C. S. Johnson, ibid. 41, 3277 (1964); R. M. Lynden-Bell, Prog. Nucl. Magn. Reson. Spectrosc. 2, 163 (1967); A. J. Vega and D. Fiat, J. Magn. Reson. 19, 21 (1974); S. Szymanski, M. Witanowski, A. Gryff-Keller, Annu. Rep. NMR Spectrosc. 8, 227 (1978).
4. E. L. Hahn and D. E. Maxwell, ibid. 88, 1070 (1952); H. S. Gutowsky, D. W. McCall, C. P. Slichter, J. Chem. Phys. 21, 279 (1953); H. M. McConnell, ibid. 28, 430 (1957); S. Alexander, ibid. 37, 967 (1962); C. S. Johnson, ibid. 41, 3277 (1964); R. M. Lynden-Bell, Prog. Nucl. Magn. Reson. Spectrosc. 2, 163 (1967); A. J. Vega and D. Fiat, J. Magn. Reson. 19, 21 (1974); S. Szymanski, M. Witanowski, A. Gryff-Keller, Annu. Rep. NMR Spectrosc. 8, 227 (1978).
5. E. L. Hahn and D. E. Maxwell, ibid. 88, 1070 (1952); H. S. Gutowsky, D. W. McCall, C. P. Slichter, J. Chem. Phys. 21, 279 (1953); H. M. McConnell, ibid. 28, 430 (1957); S. Alexander, ibid. 37, 967 (1962); C. S. Johnson, ibid. 41, 3277 (1964); R. M. Lynden-Bell, Prog. Nucl. Magn. Reson. Spectrosc. 2, 163 (1967); A. J. Vega and D. Fiat, J. Magn. Reson. 19, 21 (1974); S. Szymanski, M. Witanowski, A. Gryff-Keller, Annu. Rep. NMR Spectrosc. 8, 227 (1978).
6. E. L. Hahn and D. E. Maxwell, ibid. 88, 1070 (1952); H. S. Gutowsky, D. W. McCall, C. P. Slichter, J. Chem. Phys. 21, 279 (1953); H. M. McConnell, ibid. 28, 430 (1957); S. Alexander, ibid. 37, 967 (1962); C. S. Johnson, ibid. 41, 3277 (1964); R. M. Lynden-Bell, Prog. Nucl. Magn. Reson. Spectrosc. 2, 163 (1967); A. J. Vega and D. Fiat, J. Magn. Reson. 19, 21 (1974); S. Szymanski, M. Witanowski, A. Gryff-Keller, Annu. Rep. NMR Spectrosc. 8, 227 (1978).
7. E. L. Hahn and D. E. Maxwell, ibid. 88, 1070 (1952); H. S. Gutowsky, D. W. McCall, C. P. Slichter, J. Chem. Phys. 21, 279 (1953); H. M. McConnell, ibid. 28, 430 (1957); S. Alexander, ibid. 37, 967 (1962); C. S. Johnson, ibid. 41, 3277 (1964); R. M. Lynden-Bell, Prog. Nucl. Magn. Reson. Spectrosc. 2, 163 (1967); A. J. Vega and D. Fiat, J. Magn. Reson. 19, 21 (1974); S. Szymanski, M. Witanowski, A. Gryff-Keller, Annu. Rep. NMR Spectrosc. 8, 227 (1978).
8. E. L. Hahn and D. E. Maxwell, ibid. 88, 1070 (1952); H. S. Gutowsky, D. W. McCall, C. P. Slichter, J. Chem. Phys. 21, 279 (1953); H. M. McConnell, ibid. 28, 430 (1957); S. Alexander, ibid. 37, 967 (1962); C. S. Johnson, ibid. 41, 3277 (1964); R. M. Lynden-Bell, Prog. Nucl. Magn. Reson. Spectrosc. 2, 163 (1967); A. J. Vega and D. Fiat, J. Magn. Reson. 19, 21 (1974); S. Szymanski, M. Witanowski, A. Gryff-Keller, Annu. Rep. NMR Spectrosc. 8, 227 (1978).
9. E. L. Hahn and D. E. Maxwell, ibid. 88, 1070 (1952); H. S. Gutowsky, D. W. McCall, C. P. Slichter, J. Chem. Phys. 21, 279 (1953); H. M. McConnell, ibid. 28, 430 (1957); S. Alexander, ibid. 37, 967 (1962); C. S. Johnson, ibid. 41, 3277 (1964); R. M. Lynden-Bell, Prog. Nucl. Magn. Reson. Spectrosc. 2, 163 (1967); A. J. Vega and D. Fiat, J. Magn. Reson. 19, 21 (1974); S. Szymanski, M. Witanowski, A. Gryff-Keller, Annu. Rep. NMR Spectrosc. 8, 227 (1978).
10. L. G. Werbelow, J. Chem. Phys. 70, 5381 (1979).
11. L. Werbelow and R. E. London, Concepts Magn. Reson. 8, 325 (1996).
12. G. Binsch and H. Kessler, Angew. Chem. 19, 411 (1980); J. Jeener, Adv. Magn. Reson. 10, 1 (1982).
13. G. Binsch and H. Kessler, Angew. Chem. 19, 411 (1980); J. Jeener, Adv. Magn. Reson. 10, 1 (1982).
14. K. E. O'Hara and C. T. Slichter, J. Magn. Reson. Ser. A 109, 74 (1994); E. R. Johnston, J. S. Barber, M. Jacomet, J. C. Barborak, J. Am. Chem. Soc. 120, 1489 (1998).
15. K. E. O'Hara and C. T. Slichter, J. Magn. Reson. Ser. A 109, 74 (1994); E. R. Johnston, J. S. Barber, M. Jacomet, J. C. Barborak, J. Am. Chem. Soc. 120, 1489 (1998).
16. D. H. Jones, N. D. Kurur, D. P. Weitekamp, Bull. Magn. Reson. 14, 214 (1992).
17. F. A. L. Anet and D. I. Freedberg, Chem. Phys. Lett. 208, 187 (1993).
18. A. G. Redfield, Adv. Magn. Reson. 1, 1 (1965); A. Abragam, Principles of Nuclear Magnetism, International Series of Monographs on Physics (Clarendon, Oxford, ed. 1, 1961).
19. A. G. Redfield, Adv. Magn. Reson. 1, 1 (1965); A. Abragam, Principles of Nuclear Magnetism, International Series of Monographs on Physics (Clarendon, Oxford, ed. 1, 1961).
20. 10 s, the previously known mechanism (4) would introduce a shift of only 0.013 Hz, which is more than two orders of magnitude smaller than the experimental and calculated effects that are of interest here. The previously known dynamic frequency shifts are quadratic in the spin interactions, whereas the new dynamic terms are linear in the spin interactions.
21. D. M. Doddrell, D. T. Pegg, M. R. Bendall, J. Magn. Reson. 48, 323 (1982).
22. G. A. Morris, ibid. 80, 547 (1988).
23. A. L. Van Geet, Anal. Chem. 42, 679 (1970).
24. V. J. Basus, thesis, University of California, Los Angeles (1975).
25. M. E. Squillacote and J. M. Neth, Magn. Reson. Chem. 25, 53 (1987).
26. 1 for the proton magnetization varied from 0.3 to 0.55 s at 180 K to 0.14 to 0.25 s at 143 K. Relaxation delays between scans were varied between 2 and 8 s.
27. -1 (8, 14) but is more precise.
28. Linearity of the temperature dependence of the chemical shifts with respect to a cyclohexane reference was previously reported for the conformers of methylcyclohexane and for the related compounds cis- and trans-1,4-dimethylcyclohexane, where the chemical shifts are linear over the entire measured region of 70 K for the cis conformation and 120 K for the trans conformation (14).
29. 2 is >1 allows a quantitation of the probability that the observed deviations of the data from the best fit are consistent with the random experimental errors, the determination of which is described in the caption of Fig. 2. For the global fits presented here, 225 data points are included: 57 for the slow-exchange equilibrium constants, 16 for the fast-exchange averages, and 152 for the slow-exchange chemical shifts of the major and minor conformers.
30. -4 for the ratio of a hypothetical third conformer to that of the equatorial form, whereas a population of several percent would be needed to account for the present observations with reasonable chemical shift parameters.
31. C. Cohen-Tannoudji, J. Dupont-Roc, G. Grynberg, Atom-Photon Interactions: Basic Processes and Applications (Wiley, New York, 1992).
32. L. J. Mueller, thesis, California Institute of Technology, Pasadena (1997); L. J. Mueller and D. P. Weitekamp, in preparation.
33. L. J. Mueller, thesis, California Institute of Technology, Pasadena (1997); L. J. Mueller and D. P. Weitekamp, in preparation.
34. These contributions to the unitary evolution may be viewed as resulting from ALBATROSS. The description of the spectral densities in terms of system and bath susceptibilities (21) is not elaborated here.
35. This work was supported by NSF (grant CHE-9005964). L.J.M. acknowledges an NSF Graduate Fellowship and a Department of Defense National Defense Science and Engineering Graduate Fellowship.