Effect of Dynamical Motion in Calculations of Solid-State Nuclear Magnetic and Nuclear Quadrupole Resonance Spectra

Overview

Journal Chem Mater

Date 2024 Aug 19

PMID 39156720

Authors

Kamal Wagle

Daniel A Rehn

Ann E Mattsson

Harris E Mason

Michael W Malone

Affiliations

Soon will be listed here.

Abstract

Solid-state nuclear magnetic resonance (SSNMR) and nuclear quadrupole resonance (NQR) spectra provide detailed information about the electronic and atomic structure of solids. Modern methods such as density functional theory (DFT) can be used to calculate NMR and NQR spectra from first-principles, providing a meaningful avenue to connect theory and experiment. Prediction of SSNMR and NQR spectra from DFT relies on accurate calculation of the electric field gradient (EFG) tensor associated with the potential of electrons at the nuclear centers. While static calculations of EFGs are commonly seen in the literature, the effects of dynamical motion of atoms in molecules and solids have been less explored. In this study, we develop a method to calculate EFGs of solids while taking into account the dynamics of atoms through DFT-based molecular dynamics simulations. The method we develop is general, in the sense that it can be applied to any material at any desired temperature and pressure. Here, we focus on application of the method to NaNO and study in detail the EFGs of N, O, and Na. We find in the cases of N and O that the dynamical motion of the atoms can be used to calculate mean EFGs that are in closer agreement with experiments than those of static calculations. For Na, we find a complex behavior of the EFGs when atomic motion is incorporated that is not at all captured in static calculations. In particular, we find a distribution of EFGs that is influenced strongly by the local (changing) bond environment, with a pattern that reflects the coordination structure of Na. We expect the methodology developed here to provide a path forward for understanding materials in which static EFG calculations do not align with experiments.

References

Bernard G, Wasylishen R, Ratcliffe C, Terskikh V, Wu Q, Buriak J . Methylammonium Cation Dynamics in Methylammonium Lead Halide Perovskites: A Solid-State NMR Perspective. J Phys Chem A. 2018; 122(6):1560-1573. DOI: 10.1021/acs.jpca.7b11558. View

Charpentier T . The PAW/GIPAW approach for computing NMR parameters: a new dimension added to NMR study of solids. Solid State Nucl Magn Reson. 2011; 40(1):1-20. DOI: 10.1016/j.ssnmr.2011.04.006. View

Bylander , KLEINMAN . Energy fluctuations induced by the Nosé thermostat. Phys Rev B Condens Matter. 1992; 46(21):13756-13761. DOI: 10.1103/physrevb.46.13756. View

Trontelj Z, Luznik J, Pirnat J, Jazbinsek V, Lavric Z, Srcic S . Polymorphism in Sulfanilamide: N Nuclear Quadrupole Resonance Study. J Pharm Sci. 2019; 108(9):2865-2870. DOI: 10.1016/j.xphs.2019.05.015. View

Gohda , Ichikawa , Gustafsson , Olovsson I . X-ray study of deformation density and spontaneous polarization in ferroelectric NaNO2. Acta Crystallogr B. 2000; 56 (Pt 1):11-6. DOI: 10.1107/s010876819901054x. View

Wong Y, Landmann J, Finze M, Bryce D . Dynamic Disorder and Electronic Structures of Electron-Precise Dianionic Diboranes: Insights from Solid-State Multinuclear Magnetic Resonance Spectroscopy. J Am Chem Soc. 2017; 139(24):8200-8211. DOI: 10.1021/jacs.7b01783. View

Reif B, Ashbrook S, Emsley L, Hong M . Solid-state NMR spectroscopy. Nat Rev Methods Primers. 2021; 1. PMC: 8341432. DOI: 10.1038/s43586-020-00002-1. View

Bonhomme C, Gervais C, Babonneau F, Coelho C, Pourpoint F, Azais T . First-principles calculation of NMR parameters using the gauge including projector augmented wave method: a chemist's point of view. Chem Rev. 2012; 112(11):5733-79. DOI: 10.1021/cr300108a. View

Unzueta P, Greenwell C, Beran G . Predicting Density Functional Theory-Quality Nuclear Magnetic Resonance Chemical Shifts via Δ-Machine Learning. J Chem Theory Comput. 2021; 17(2):826-840. DOI: 10.1021/acs.jctc.0c00979. View

10.

Dumez J, Pickard C . Calculation of NMR chemical shifts in organic solids: accounting for motional effects. J Chem Phys. 2009; 130(10):104701. DOI: 10.1063/1.3081630. View

11.

Piveteau L, Morad V, Kovalenko M . Solid-State NMR and NQR Spectroscopy of Lead-Halide Perovskite Materials. J Am Chem Soc. 2020; 142(46):19413-19437. PMC: 7677932. DOI: 10.1021/jacs.0c07338. View

12.

Togo A, Chaput L, Tadano T, Tanaka I . Implementation strategies in phonopy and phono3py. J Phys Condens Matter. 2023; 35(35). DOI: 10.1088/1361-648X/acd831. View

13.

Kresse , Hafner . Ab initio molecular dynamics for liquid metals. Phys Rev B Condens Matter. 1993; 47(1):558-561. DOI: 10.1103/physrevb.47.558. View

14.

Malone M, Espy M, He S, Janicke M, Williams R . The H T dispersion curve of fentanyl citrate to identify NQR parameters. Solid State Nucl Magn Reson. 2020; 110:101697. DOI: 10.1016/j.ssnmr.2020.101697. View

15.

Laws D, Bitter H, Jerschow A . Solid-state NMR spectroscopic methods in chemistry. Angew Chem Int Ed Engl. 2002; 41(17):3096-129. DOI: 10.1002/1521-3773(20020902)41:17<3096::AID-ANIE3096>3.0.CO;2-X. View

16.

SCHWARZ , BLAHA . Charge distribution and electric-field gradients in YBa2Cu3O7-x. Phys Rev B Condens Matter. 1990; 42(4):2051-2061. DOI: 10.1103/physrevb.42.2051. View

17.

Dracinsky M, Bour P, Hodgkinson P . Temperature Dependence of NMR Parameters Calculated from Path Integral Molecular Dynamics Simulations. J Chem Theory Comput. 2016; 12(3):968-73. DOI: 10.1021/acs.jctc.5b01131. View

18.

Latosinska J . Nuclear quadrupole resonance spectroscopy in studies of biologically active molecular systems--a review. J Pharm Biomed Anal. 2005; 38(4):577-87. DOI: 10.1016/j.jpba.2005.03.030. View

19.

Dracinsky M, Hodgkinson P . Effects of quantum nuclear delocalisation on NMR parameters from path integral molecular dynamics. Chemistry. 2014; 20(8):2201-7. DOI: 10.1002/chem.201303496. View

20.

Dracinsky M, Bour P . Vibrational averaging of the chemical shift in crystalline α-glycine. J Comput Chem. 2012; 33(10):1080-9. DOI: 10.1002/jcc.22940. View