Multidimensional Rietveld Refinement of High-pressure Neutron Diffraction Data of PbNCN

Overview

Journal J Appl Crystallogr

Date 2024 Oct 10

PMID 39387076

Authors

Yannick Meinerzhagen

Katharina Eickmeier

Peter C Muller

Jan Hempelmann

Andreas Houben

Richard Dronskowski

Affiliations

Soon will be listed here.

Abstract

High-pressure neutron powder diffraction data from PbNCN were collected on the high-pressure diffraction beamline SNAP located at the Spallation Neutron Source (SNS) of Oak Ridge National Laboratory (Tennessee, USA). The diffraction data were analyzed using the novel method of multidimensional (two dimensions for now, potentially more in the future) Rietveld refinement and, for comparison, employing the conventional Rietveld method. To achieve two-dimensional analysis, a detailed description of the SNAP instrument characteristics was created, serving as an instrument parameter file, and then yielding both cell and spatial parameters as refined under pressure for the first time for solid-state cyanamides/carbodi-imides. The bulk modulus = 25.1 (15) GPa and its derivative ' = 11.1 (8) were extracted for PbNCN following the Vinet equation of state. Surprisingly, an internal transition was observed beyond 2.0 (2) GPa, resulting from switching the bond multiplicities (and bending direction) of the NCN complex anion. The results were corroborated using electronic structure calculation from first principles, highlighting both local structural and chemical bonding details.

References

Huq A, Kirkham M, Peterson P, Hodges J, Whitfield P, Page K . POWGEN: rebuild of a third-generation powder diffractometer at the Spallation Neutron Source. J Appl Crystallogr. 2019; 52(Pt 5):1189-1201. PMC: 6782079. DOI: 10.1107/S160057671901121X. View

Calder S, An K, Boehler R, Dela Cruz C, Frontzek M, Guthrie M . A suite-level review of the neutron powder diffraction instruments at Oak Ridge National Laboratory. Rev Sci Instrum. 2018; 89(9):092701. DOI: 10.1063/1.5033906. View

Jacobs P, Houben A, Schweika W, Tchougreeff A, Dronskowski R . Instrumental resolution as a function of scattering angle and wavelength as exemplified for the POWGEN instrument. J Appl Crystallogr. 2017; 50(Pt 3):866-875. PMC: 5458595. DOI: 10.1107/S1600576717005398. View

Maintz S, Deringer V, Tchougreeff A, Dronskowski R . LOBSTER: A tool to extract chemical bonding from plane-wave based DFT. J Comput Chem. 2016; 37(11):1030-5. PMC: 5067632. DOI: 10.1002/jcc.24300. View

Liu X, Muller P, Kroll P, Dronskowski R, Wilsmann W, Conradt R . Experimental and quantum-chemical studies on the thermochemical stabilities of mercury carbodiimide and mercury cyanamide. Chemphyschem. 2003; 4(7):725-31. DOI: 10.1002/cphc.200300635. View

Grimme S, Antony J, Ehrlich S, Krieg H . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. 2010; 132(15):154104. DOI: 10.1063/1.3382344. View

Grimme S, Ehrlich S, Goerigk L . Effect of the damping function in dispersion corrected density functional theory. J Comput Chem. 2011; 32(7):1456-65. DOI: 10.1002/jcc.21759. View

Kresse , Furthmuller . Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B Condens Matter. 1996; 54(16):11169-11186. DOI: 10.1103/physrevb.54.11169. View

Blochl . Projector augmented-wave method. Phys Rev B Condens Matter. 1994; 50(24):17953-17979. DOI: 10.1103/physrevb.50.17953. View

10.

Blochl , Jepsen , Andersen . Improved tetrahedron method for Brillouin-zone integrations. Phys Rev B Condens Matter. 1994; 49(23):16223-16233. DOI: 10.1103/physrevb.49.16223. View

11.

Jacobs P, Houben A, Schweika W, Tchougreeff A, Dronskowski R . A Rietveld refinement method for angular- and wavelength-dispersive neutron time-of-flight powder diffraction data. J Appl Crystallogr. 2015; 48(Pt 6):1627-1636. PMC: 4665658. DOI: 10.1107/S1600576715016520. View

12.

Maintz S, Deringer V, Tchougreeff A, Dronskowski R . Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids. J Comput Chem. 2013; 34(29):2557-67. DOI: 10.1002/jcc.23424. View

13.

Nelson R, Ertural C, George J, Deringer V, Hautier G, Dronskowski R . LOBSTER: Local orbital projections, atomic charges, and chemical-bonding analysis from projector-augmented-wave-based density-functional theory. J Comput Chem. 2020; 41(21):1931-1940. DOI: 10.1002/jcc.26353. View

14.

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

15.

VINET , Smith , Ferrante , Rose . Temperature effects on the universal equation of state of solids. Phys Rev B Condens Matter. 1987; 35(4):1945-1953. DOI: 10.1103/physrevb.35.1945. View

16.

Houben A, Meinerzhagen Y, Nachtigall N, Jacobs P, Dronskowski R . POWTEX visits POWGEN. J Appl Crystallogr. 2023; 56(Pt 3):633-642. PMC: 10241063. DOI: 10.1107/S1600576723002819. View