Mechanistic origins of methyl-driven Overhauser DNP

Perras, Frédéric A.; Matsuki, Yoh; Southern, Scott A.; Dubroca, Thierry; Flesariu, Dragos F.; Van Tol, Johan; Constantinides, Christos P.; Koutentis, Panayiotis A.

doi:10.1063/5.0149664

Mechanistic origins of methyl-driven Overhauser DNP

Journal Article · Fri Apr 21 00:00:00 EDT 2023 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0149664· OSTI ID:1972802

^[1]; ^[2]; ^[1]; ^[3]; Flesariu, Dragos F. ^[4]; ^[3]; ^[5]; ^[4]

Ames Lab., and Iowa State Univ., Ames, IA (United States)
Iowa State Univ., Ames, IA (United States); Osaka Univ. (Japan)
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
University of Cyprus, Nicosia (Cyprus)
University of Michigan-Dearborn, MI (United States)

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. Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: Japan Society for the Promotion of Science (JSPS); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1972802

Alternate ID(s):: OSTI ID: 1970551

Report Number(s):: IS-J 11,053

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 15 Vol. 158; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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