Electron spin relaxation due to reorientation of a permanent zero field splitting tensor
dc.contributor.author | Schaefle, Nathaniel | en_US |
dc.contributor.author | Sharp, Robert R. | en_US |
dc.date.accessioned | 2010-05-06T22:50:13Z | |
dc.date.available | 2010-05-06T22:50:13Z | |
dc.date.issued | 2004-09-15 | en_US |
dc.identifier.citation | Schaefle, Nathaniel; Sharp, Robert (2004). "Electron spin relaxation due to reorientation of a permanent zero field splitting tensor." The Journal of Chemical Physics 121(11): 5387-5394. <http://hdl.handle.net/2027.42/70866> | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/70866 | |
dc.identifier.uri | http://www.ncbi.nlm.nih.gov/sites/entrez?cmd=retrieve&db=pubmed&list_uids=15352832&dopt=citation | en_US |
dc.description.abstract | Electron spin relaxation of transition metal ions with spin S ≥ 1S⩾1 results primarily from thermal modulation of the zero field splitting (zfs) tensor. This occurs both by distortion of the zfs tensor due to intermolecular collisions and, for complexes with less than cubic symmetry, by reorientational modulation of the permanent zfs tensor. The reorientational mechanism is much less well characterized in previous work than the distortional mechanism although it is an important determinant of nuclear magnetic resonance (NMR) paramagnetic relaxation enhancement phenomena (i.e., the enhancement of NMR relaxation rates produced by paramagnetic ions in solution or NMR-PRE). The classical density matrix theory of spin relaxation does not provide an appropriate description of the reorientational mechanism at low Zeeman field strengths because the zero-order spin wave functions are stochastic functions of time. Using spin dynamics simulation techniques, the time correlation functions of the spin operators have been computed and used to determine decay times for the reorientational relaxation mechanism for S = 1.S=1. In the zfs limit of laboratory field strengths (HZeem≪Hzfs∘),(HZeem≪Hzfs∘), when the zfs tensor is cylindrical, the spin decay is exponential, the spin relaxation time, τS∘ ≈ 0.53τR(1),τS∘≈0.53τR(1), where τR(1)τR(1) is the reorientational correlation time of a molecule-fixed vector. The value of τS∘τS∘ is independent of the magnitude of the cylindrical zfs parameter (D), but it depends strongly on low symmetry zfs terms (the E/DE/D ratio). Other spin dynamics (SD) simulations examined spin decay in the intermediate regime of field strengths where HZeem ≈ Hzfs∘,HZeem≈Hzfs∘, and in the vicinity of the Zeeman limit. The results demonstrate that the reorientational electron spin relaxation mechanism is often significant when Hzfs∘ ≥ HZeem,Hzfs∘⩾HZeem, and that its neglect can lead to serious errors in the interpretation of NMR-PRE data. © 2004 American Institute of Physics. | en_US |
dc.format.extent | 3102 bytes | |
dc.format.extent | 160662 bytes | |
dc.format.mimetype | text/plain | |
dc.format.mimetype | application/octet-stream | |
dc.publisher | The American Institute of Physics | en_US |
dc.rights | © The American Institute of Physics | en_US |
dc.title | Electron spin relaxation due to reorientation of a permanent zero field splitting tensor | en_US |
dc.type | Article | en_US |
dc.subject.hlbsecondlevel | Physics | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 | en_US |
dc.identifier.pmid | 15352832 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/70866/2/JCPSA6-121-11-5387-1.pdf | |
dc.identifier.doi | 10.1063/1.1786577 | en_US |
dc.identifier.source | The Journal of Chemical Physics | en_US |
dc.identifier.citedreference | J. H. Van Vleck, Phys. Rev. PHRVAO57, 426 (1940). | en_US |
dc.identifier.citedreference | N. Bloembergen and L. O. Morgan, J. Chem. Phys. JCPSA634, 842 (1961). | en_US |
dc.identifier.citedreference | A. Carrington and G. R. Luckhurst, Mol. Phys. MOPHAM8, 125 (1964). | en_US |
dc.identifier.citedreference | M. Rubinstein, A. Baram, and Z. Luz, Mol. Phys. MOPHAM20, 67 (1971). | en_US |
dc.identifier.citedreference | B. B. Garrett and L. O. Morgan, J. Chem. Phys. JCPSA644, 890 (1966). | en_US |
dc.identifier.citedreference | G. R. Luckhurst and G. F. Pedulli, Mol. Phys. MOPHAM22, 931 (1971). | en_US |
dc.identifier.citedreference | P.-O. Westlund, N. Benetis, and H. Wennerstrom, Mol. Phys. MOPHAM61, 177 (1987). | en_US |
dc.identifier.citedreference | J. Svoboda, T. Nilsson, J. Kowalewski, P.-O. Westlund, and P. T. Larsson, J. Magn. Reson., Ser. A JMRAE2121, 108 (1996). | en_US |
dc.identifier.citedreference | P.-O. Westlund and P. T. Larsson, Acta Chem. Scand. ACHSE745, 11 (1991). | en_US |
dc.identifier.citedreference | P.-O. Westlund, J. Chem. Phys. JCPSA6108, 4945 (1998). | en_US |
dc.identifier.citedreference | I. Bertini, J. Kowalewski, C. Luchinat, T. Nilsson, and G. Parigi, J. Chem. Phys. JCPSA6111, 5795 (1999). | en_US |
dc.identifier.citedreference | R. Sharp and L. Lohr, J. Chem. Phys. JCPSA6115, 5005 (2001). | en_US |
dc.identifier.citedreference | R. Sharp, J. Magn. Reson. JMARF3154, 269 (2002). | en_US |
dc.identifier.citedreference | A. Hudson and G. R. Luckhurst, Mol. Phys. MOPHAM16, 395 (1969). | en_US |
dc.identifier.citedreference | A. Hudson and J. W. E. Lewis, Trans. Faraday Soc. TFSOA466, 1297 (1970). | en_US |
dc.identifier.citedreference | A. D. McLachlan, Proc. R. Soc. London PRLBA4280, 271 (1964). | en_US |
dc.identifier.citedreference | H. Levanon, S. Charbinsky, and Z. Luz, J. Chem. Phys. JCPSA653, 3056 (1970). | en_US |
dc.identifier.citedreference | S. Rast, A. Borel, L. Helm, E. Belorizky, P. H. Fries, and A. E. Merbach, J. Am. Chem. Soc. JACSAT123, 2637 (2001). | en_US |
dc.identifier.citedreference | S. Rast, P. H. Fries, and E. Belorizky, J. Chem. Phys. JCPSA6113, 8724 (2000). | en_US |
dc.identifier.citedreference | R. Sharp, Nucl. Magn. Reson., Spec. Period. Rep.ZZZZZZ 30, 477 (2001); 32, 473 (2003). | en_US |
dc.identifier.citedreference | E. Toth, L. Helm, and A. E. Merbach, Comprehensive Coord. Chem. II ZZZZZZ9, 841 (2004). | en_US |
dc.identifier.citedreference | N. Benetis, J. Kowalewski, L. Nordenskiold, H. Wennerstrom, and P.-O. Westlund, Mol. Phys. MOPHAM48, 329 (1983). | en_US |
dc.identifier.citedreference | N. Benetis, J. Kowalewski, L. Nordenskiold, H. Wennerstrom, and P.-O. Westlund, J. Magn. Reson. (1969-1992) JOMRA458, 261 (1984). | en_US |
dc.identifier.citedreference | P.-O. Westlund, H. Wennerstrom, L. Nordenskiold, J. Kowalewski, and N. Benetis, J. Magn. Reson. (1969-1992) JOMRA459, 91 (1984). | en_US |
dc.identifier.citedreference | N. Benetis, J. Kowalewski, L. Nordenskiold, H. Wennerstrom, and P.-O. Westlund, Mol. Phys. MOPHAM50, 515 (1983). | en_US |
dc.identifier.citedreference | J. Kowalewski, L. Nordenskiold, N. Benetis, and P.-O. Westlund, Prog. Nucl. Magn. Reson. Spectrosc. PNMRAT17, 141 (1985). | en_US |
dc.identifier.citedreference | An earlier version of the program called SpinDyn is described by S. M. Abernathy and R. R. Sharp, J. Chem. Phys. JCPSA6106, 9032 (1997). | en_US |
dc.identifier.citedreference | E. N. Ivanov, Zh. Eksp. Teor. Fiz. 45, 1509 (1963) [Sov. Phys. JETP SPHJAR18, 1041 (1964). | en_US |
dc.identifier.citedreference | M. Odelius, C. Ribbing, and J. Kowalewski, J. Chem. Phys. JCPSA6103, 1800 (1995). | en_US |
dc.identifier.citedreference | J. Miller, N. Schaefle, and R. Sharp, Magn. Reson. Chem. MRCHEG41, 806 (2003). | en_US |
dc.identifier.citedreference | A. Messiah, Quantum Mechanics (Wiley, New York, 1962), Chap. XVII. | en_US |
dc.identifier.citedreference | S. M. Blinder, Foundations of Quantum Mechanics (Academic, New York, 1974), Chap. 7. | en_US |
dc.identifier.citedreference | R. Sharp, L. Lohr, and J. Miller, Prog. Nucl. Magn. Reson. Spectrosc. PNMRAT38, 115 (2001). | en_US |
dc.identifier.citedreference | I. Bertini, C. Luchinat, and J. Kowalewski, J. Magn. Reson. (1969-1992) JOMRA462, 235 (1985). | en_US |
dc.identifier.citedreference | J. C. Miller and R. R. Sharp, J. Phys. Chem. A JPCAFH104, 4889 (2000). | en_US |
dc.identifier.citedreference | P.-O. Westlund, in Dynamics of Solutions and Fluid Mixtures by NMR, edited by J. J. Delpuech (Wiley, New York, 1995), p. 173. | en_US |
dc.identifier.citedreference | T. Nilsson and J. Kowalewski, J. Magn. Reson. JMARF3146, 345 (2000). | en_US |
dc.identifier.citedreference | D. Kruk, T. Nilsson, and J. Kowalewski, Phys. Chem. Chem. Phys. PPCPFQ3, 4907 (2001). | en_US |
dc.identifier.citedreference | R. Nilsson, J. Svoboda, P.-O. Westlund, and J. Kowalewski, J. Chem. Phys. JCPSA6109, 6364 (1998). | en_US |
dc.identifier.citedreference | R. R. Sharp, J. Chem. Phys. JCPSA693, 6921 (1990). | en_US |
dc.identifier.citedreference | R. R. Sharp, J. Magn. Reson. (1969-1992) JOMRA4100, 491 (1992). | en_US |
dc.identifier.citedreference | R. Sharp, S. M. Abernathy, and L. L. Lohr, J. Chem. Phys. JCPSA6107, 7620 (1997). | en_US |
dc.identifier.citedreference | I. Bertini, O. Galas, C. Luchinat, and G. Parigi, J. Magn. Reson., Ser. A JMRAE2113, 151 (1995). | en_US |
dc.identifier.citedreference | J. Kowalewski, C. Luchinat, T. Nilsson, and G. Parigi, J. Phys. Chem. A JPCAFH106, 7376 (2002). | en_US |
dc.identifier.citedreference | D. Kruk and J. Kowalewski, JBIC, J. Biol. Inorg. Chem. JJBCFA8, 512 (2003). | en_US |
dc.identifier.citedreference | T. Nilsson and J. Kowalewski, Mol. Phys. MOPHAM98, 1617 (2000). | en_US |
dc.identifier.citedreference | R. R. Sharp, J. Chem. Phys. JCPSA698, 6092 (1993). | en_US |
dc.identifier.citedreference | S. M. Abernathy, J. C. Miller, L. L. Lohr, and R. R. Sharp, J. Chem. Phys. JCPSA6109, 4035 (1998). | en_US |
dc.identifier.citedreference | J. C. Miller, L. L. Lohr, and R. R. Sharp, J. Magn. Reson. JMARF3148, 267 (2001). | en_US |
dc.owningcollname | Physics, Department of |
Files in this item
Remediation of Harmful Language
The University of Michigan Library aims to describe library materials in a way that respects the people and communities who create, use, and are represented in our collections. Report harmful or offensive language in catalog records, finding aids, or elsewhere in our collections anonymously through our metadata feedback form. More information at Remediation of Harmful Language.
Accessibility
If you are unable to use this file in its current format, please select the Contact Us link and we can modify it to make it more accessible to you.