Revisiting the Van Vleck second moment for characterizing molecular motion in organic solids

Sturniolo, Simone; Wickins, Helen M.; Hodgkinson, Paul

Abstract

Van Vleck’s classic theory of the second moment of lineshapes in 1H nuclear magnetic resonance (NMR) is reworked in a form that allows the effect of rapid molecular motion on second moments to be calculated in a semi-analytical fashion. This is much more efficient than existing approaches and also extends previous analyses of (non-dynamic) dipolar networks in terms of site-specific root-sum-square dipolar couplings. The non-local nature of the second moment means that it can discriminate between overall motions that are difficult to discriminate using alternative approaches, such as measurements of NMR relaxation. The value of reviving second moment studies is illustrated on the plastic solids diamantane and triamantane. In the case of triamantane, straightforward measurements of 1H lineshapes on milligram samples show that the molecules in the higher temperature phase undergo multi-axis jumps, information that is not accessible either to diffraction studies or to alternative NMR approaches. The efficiency of the computational methods means that the second moments can be calculated using a readily extensible and open-source Python code.

Citation

Sturniolo, S., Wickins, H. M., & Hodgkinson, P. (2023). Revisiting the Van Vleck second moment for characterizing molecular motion in organic solids. The Journal of Chemical Physics, 158(24), https://doi.org/10.1063/5.0151022

• Journal Article Type: Article
• Acceptance Date: Jun 7, 2023
• Online Publication Date: Jun 26, 2023
• Publication Date: Jun 28, 2023
• Deposit Date: Aug 17, 2023
• Publicly Available Date: Aug 17, 2023
• Journal: The Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 158
• Issue: 24
• DOI: https://doi.org/10.1063/5.0151022
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://durham-repository.worktribe.com/output/1720523