Out-of-phase PELDOR
Abstract
Pulsed electron-electron double resonance (PELDOR) is a method frequently used to determine the structure of bio-macromolecule on a nanometre scale. Usually PELDOR experiments are carried out in the high-temperature limit, when the Boltzmann population of spins oriented parallel and antiparallel to the external magnetic field are almost equal. Also the well-developed theories describing PELDOR apply to this case. However, the high-temperature conditions are no more fulfilled for experiments done in a high magnetic field (above 6 T) and at low temperatures (below 5 K), when the Zeeman interaction energy of an electron spin becomes comparable with thermal energy ?. In this work we demonstrate that PELDOR signals measured at these conditions differ from the usual PELDOR signals. Additional to the standard in-phase component the PELDOR signal at low temperature and high magnetic field also contains an out-of-phase component that disappears in the high-temperature limit. This means that we observe not only the modulation of the refocused transverse magnetisation along a single axis in the rotating coordinate system but rather its precession in the x-y plane with a dipolar frequency. Here, we provide a quantitative explanation as well as a detailed analysis of the spin magnetisation dynamics under such conditions based on density matrix formalism. Understanding the PELDOR phenomena in high field and at low temperatures offers a tool to separate intra from intermolecular interactions, which might be extremely helpful and important for applications to biomolecules with a high degree of conformational flexibility.
- Publication:
-
Molecular Physics
- Pub Date:
- October 2013
- DOI:
- 10.1080/00268976.2013.807369
- Bibcode:
- 2013MolPh.111.2834M
- Keywords:
-
- EPR;
- PELDOR;
- DEER;
- high field;
- out-of-phase