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Longitudinal relaxation in dipole-coupled homonuclear three-spin systems: Distinct correlations and odd spectral densities.

Chang, Zhiwei LU and Halle, Bertil LU (2015) In Journal of Chemical Physics 143(23).
Abstract
A system of three dipole-coupled spins exhibits a surprisingly intricate relaxation behavior. Following Hubbard's pioneering 1958 study, many authors have investigated different aspects of this problem. Nevertheless, on revisiting this classic relaxation problem, we obtain several new results, some of which are at variance with conventional wisdom. Most notably from a fundamental point of view, we find that the odd-valued spectral density function influences longitudinal relaxation. We also show that the effective longitudinal relaxation rate for a non-isochronous three-spin system can exhibit an unusual inverted dispersion step. To clarify these and other issues, we present a comprehensive theoretical treatment of longitudinal relaxation... (More)
A system of three dipole-coupled spins exhibits a surprisingly intricate relaxation behavior. Following Hubbard's pioneering 1958 study, many authors have investigated different aspects of this problem. Nevertheless, on revisiting this classic relaxation problem, we obtain several new results, some of which are at variance with conventional wisdom. Most notably from a fundamental point of view, we find that the odd-valued spectral density function influences longitudinal relaxation. We also show that the effective longitudinal relaxation rate for a non-isochronous three-spin system can exhibit an unusual inverted dispersion step. To clarify these and other issues, we present a comprehensive theoretical treatment of longitudinal relaxation in a three-spin system of arbitrary geometry and with arbitrary rotational dynamics. By using the Liouville-space formulation of Bloch-Wangsness-Redfield theory and a basis of irreducible spherical tensor operators, we show that the number of relaxation components in the different cases can be deduced from symmetry arguments. For the isochronous case, we present the relaxation matrix in analytical form, whereas, for the non-isochronous case, we employ a computationally efficient approach based on the stochastic Liouville equation. (Less)
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organization
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Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
143
issue
23
publisher
American Institute of Physics
external identifiers
  • pmid:26696052
  • scopus:84951165691
  • wos:000369806500015
ISSN
0021-9606
DOI
10.1063/1.4937377
language
English
LU publication?
yes
id
9fd58d78-b70c-479a-81fe-a9e8c25106a5 (old id 8503875)
date added to LUP
2016-01-07 17:11:21
date last changed
2017-05-21 03:27:10
@article{9fd58d78-b70c-479a-81fe-a9e8c25106a5,
  abstract     = {A system of three dipole-coupled spins exhibits a surprisingly intricate relaxation behavior. Following Hubbard's pioneering 1958 study, many authors have investigated different aspects of this problem. Nevertheless, on revisiting this classic relaxation problem, we obtain several new results, some of which are at variance with conventional wisdom. Most notably from a fundamental point of view, we find that the odd-valued spectral density function influences longitudinal relaxation. We also show that the effective longitudinal relaxation rate for a non-isochronous three-spin system can exhibit an unusual inverted dispersion step. To clarify these and other issues, we present a comprehensive theoretical treatment of longitudinal relaxation in a three-spin system of arbitrary geometry and with arbitrary rotational dynamics. By using the Liouville-space formulation of Bloch-Wangsness-Redfield theory and a basis of irreducible spherical tensor operators, we show that the number of relaxation components in the different cases can be deduced from symmetry arguments. For the isochronous case, we present the relaxation matrix in analytical form, whereas, for the non-isochronous case, we employ a computationally efficient approach based on the stochastic Liouville equation.},
  articleno    = {234201},
  author       = {Chang, Zhiwei and Halle, Bertil},
  issn         = {0021-9606},
  language     = {eng},
  number       = {23},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Longitudinal relaxation in dipole-coupled homonuclear three-spin systems: Distinct correlations and odd spectral densities.},
  url          = {http://dx.doi.org/10.1063/1.4937377},
  volume       = {143},
  year         = {2015},
}