Mechanistic origins of methyl-driven Overhauser DNP

The Overhauser effect in the dynamic nuclear polarization (DNP) of non-conducting solids has drawn much attention due to the potential for efficient high-field DNP as well as a general interest in the underlying principles that enable the Overhauser effect in small molecules. We recently reported th...

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Veröffentlicht in:The Journal of chemical physics 2023-04, Vol.158 (15)
Hauptverfasser: Perras, Frédéric A., Matsuki, Yoh, Southern, Scott A., Dubroca, Thierry, Flesariu, Dragos F., Van Tol, Johan, Constantinides, Christos P., Koutentis, Panayiotis A.
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container_issue 15
container_start_page
container_title The Journal of chemical physics
container_volume 158
creator Perras, Frédéric A.
Matsuki, Yoh
Southern, Scott A.
Dubroca, Thierry
Flesariu, Dragos F.
Van Tol, Johan
Constantinides, Christos P.
Koutentis, Panayiotis A.
description The Overhauser effect in the dynamic nuclear polarization (DNP) of non-conducting solids has drawn much attention due to the potential for efficient high-field DNP as well as a general interest in the underlying principles that enable the Overhauser effect in small molecules. We recently reported the observation of 1H and 2H Overhauser effects in H3C- or D3C-functionalized Blatter radical analogs, which we presumed to be caused by methyl rotation. In this work, we look at the mechanism for methyl-driven Overhauser DNP in greater detail, considering methyl librations and tunneling in addition to classical rotation. We predict the temperature dependence of these mechanisms using density functional theory and spin dynamics simulations. Comparisons with results from ultralow-temperature magic angle spinning-DNP experiments revealed that cross-relaxation at temperatures above 60 K originates from both libration and rotation, while librations dominate at lower temperatures. Due to the zero-point vibrational nature of these motions, they are not quenched by very low temperatures, and methyl-driven Overhauser DNP is expected to increase in efficiency down to 0 K, predominantly due to increases in nuclear relaxation times.
doi_str_mv 10.1063/5.0149664
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subjects Cross relaxation
Density functional theory
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Libration
Low temperature
Nuclear relaxation
Overhauser effect
Rotation
Spin dynamics
Temperature dependence
title Mechanistic origins of methyl-driven Overhauser DNP
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