Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Submitted Manuscript

Publication Date

5-26-2020

Journal or Book Title

The Journal of Physical Chemistry Letters

Volume

11

Issue

14

First Page

5655

Last Page

5660

DOI

10.1021/acs.jpclett.0c00955

Abstract

Theoretical models aimed at describing magic-angle-spinning (MAS) dynamic nuclear polarization (DNP) NMR typically face a trade-off between the scientific rigor obtained with a strict quantum mechanical description, and the need for using realistically large spin systems, for instance using phenomenological models. Thus far, neither approach has accurately reproduced experimental results, let alone achieved the generality required to act as a reliable predictive tool. Here, we show that the use of aggressive state-space restrictions and an optimization strategy allows full-scale ab initio MAS-DNP simulations of spin systems containing thousands of nuclei. Our simulations are the first ever to achieve quantitative reproduction of experimental DNP enhancements and their MAS rate dependence for both frozen solutions and solid materials. They also revealed the importance of a previously unrecognized structural feature found in some polarizing agents that helps minimize the sensitivity losses imposed by the spin diffusion barrier.

Comments

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.jpclett.0c00955. Posted with permission.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Published Version

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