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@MISC{ValenzuelaReina:1046220,
      author       = {Valenzuela Reina, Javier and Barysch, Vera and Szczuka,
                      Conrad and Köcher, Simone Swantje and Granwehr, Josef and
                      Scheurer, Christoph},
      title        = {{R}eplication {D}ata for: {D}ecoding the {A}l{PO}4 and
                      {LATP} surface with a combined {NMR}-{DFT} approach},
      publisher    = {Jülich DATA},
      reportid     = {FZJ-2025-03756},
      year         = {2025},
      abstract     = {Replication Data for: Decoding the AlPO4 and LATP surface
                      with a combined NMR-DFT approach Supporting experimental and
                      DFT data for the publication. In the accompanying
                      publication, we combine advanced nuclear magnetic resonance
                      (NMR) experiments and density functional theory (DFT)
                      simulations to study AlPO4 as a model for the surface of the
                      well-known solid ion conductor Li1+xAlxTi2-x(PO4)3 with 0.3
                      ≤ x ≤ 0.5 (LATP), which is a promising candidate for the
                      ceramic component of a hybrid electrolyte. By combining the
                      multi-nuclei NMR techniques cross-polarization (CP) and
                      transfer of populations in double resonance (TRAPDOR) on
                      AlPO4 powder with DFT calculations of NMR observables for a
                      variety of surface models, the surface structure of
                      commercial AlPO4 is elucidated. It is shown that even after
                      extended drying, the surface of AlPO4 is hydroxylated with a
                      TRAPDOR-estimated 1H-27Al quadrupolar coupling constant, CQ,
                      of 5.8 ± 0.9 MHz. The joint theoretical--experimental
                      approach also enables first insights into the bonding motifs
                      of organic entities on functionalized AlPO4 surfaces as a
                      model for the LATP surfaces, which confirm surface
                      interactions and the presence of silane on both
                      functionalized AlPO4 and LATP. We demonstrate that
                      observables, that are experimentally as well as
                      theoretically accessible, provide information on interfacial
                      bonding motifs, interatomic distances, and interactions,
                      surpassing the capabilities of either NMR or DFT techniques
                      alone. The dataset contains the experimental NMR and EDX
                      data as well as the atomistic structure models and the
                      corresponding DFT simulations of NMR observables. 1H, 6Li,
                      31P, and 27Al NMR measurements were conducted on a Bruker
                      Avance III HD spectrometer with a 9.4 T magnet. A 3.2 mm
                      triple resonance H/X/Y CPMAS probe was used for all samples.
                      All measurements took place with a probe temperature of 20
                      °C. The working frequencies were 400.2 MHz for 1H, 58.9 MHz
                      for 6Li, 162.0 MHz for 31P, and 104.3 MHz for 27Al. No
                      decoupling was used in the pulse sequence. The samples were
                      measured at a spinning frequency of 20 kHz if not stated
                      differently. The EDX measurements were conducted on a Quanta
                      FEG 650 scanning electron microscope (FEI), equipped with
                      additional energy-dispersive X-ray spectroscopy equipment
                      (SEM-EDX). An Everhard Thornley detector was used to detect
                      the secondary electrons. DFT calculations were conducted
                      using the plane wave, pseudopotential electronic structure
                      code CASTEP v.23. In this work, the C19 family of
                      pseudopotentials was used that, in the case of Al and P,
                      treats the 3s and 3p electrons explicitly. The
                      Perdew-Burke-Ernzerhof (PBE) exchange correlation functional
                      was employed for all the calculations. NMR observables were
                      calculated with the GIPAW method as implemented in CASTEP
                      v.23 with on-the-fly generated GIPAW pseudopotentials. For
                      further details, please refer to the related open source
                      publication and Supplementary Information. Please, switch to
                      Tree View for the folder structure. The folder NMR contains
                      the primary NMR data as Bruker files $NMR/Bruker_files$ as
                      well as the analyzed, secondary data NMR/Analysis in
                      comma-separated CSV format, which is the basis for the
                      figures in the related publication. The first line in the
                      CSV files defines the parameter, the second the
                      corresponding unit.
                      $NMR/Analysis/MAS_NMR_AlPO4_drying_series/Individual_fits_AlPO4_drying_series$
                      also includes the fitting parameters for the pseudo-Voigt
                      fits of the 1H and 27Al NMR measurements of commercial AlPO4
                      as well as dried AlPO4 samples with different drying times.
                      The first row represents the drying time and the
                      corresponding errors, while the fitting parameters are
                      specified in the first column. 31P MAS NMR spectra without
                      CP were normalized by dividing the signal intensity by the
                      respective absolute integral, while 27Al MAS NMR spectra
                      were normalized by dividing by the respective total integral
                      and 1H MAS NMR spectra were divided by the rotor content
                      mass. 31P{1H} CP spectra were normalized to the maximum
                      intensity. The TRAPDOR raw data is provided with the
                      frequency offset O2 as a file title, for example the file
                      name $'minus_2_0_MHz'$ corresponds to O2 = -2.0 MHz. The
                      TRAPDOR pulse program was kindly provided by former
                      colleagues of the authors from the Lab of Prof. Clare Grey.
                      The following experiments are included
                      $MAS_NMR_AlPO4_drying_series$ 1H, 31P, and 27Al NMR
                      measurements of commercial AlPO4 as well as dried AlPO4
                      samples with different drying times.
                      $MAS_31P_1H_CP_AlPO4_dried$ 31P{1H} CP spectra with
                      different contact times. $TRAPDOR_27Al_1H_AlPO4_dried$
                      TRAPDOR spectra with different frequency offsets O2.
                      $MAS_1H_TMPES$ 1H NMR spectrum of pure
                      trimethoxy-(2-phenylethyl)silane (TMPES).
                      $MAS_1H_AlPO4_silanized$ 1H MAS NMR spectrum of TMPES
                      silanized dried AlPO4. $MAS_1H_LATP_silanized$ 1H MAS NMR
                      spectrum of TMPES silanized LATP. $MAS_NMR_LATP/MAS_X_LATP$
                      where X specifies the nucleus; 6Li, 27Al, and 31P MAS NMR
                      spectra of LATP. The folder EDX contains the original EDX
                      data $_raw.txt$ as well as the spectra $_spectrum.csv.$ The
                      spectra of the pure silane TMPES and the silanized ceramics
                      were normalized to the maximum signal intensity. The folder
                      DFT contains the atomic coordinates (xyz and cif files) of
                      the structure models discussed in the related publication.
                      The DFT output files .castep contain all the CASTEP
                      calculation parameters and settings as well as the output
                      quantities energy and NMR observables, while .magres
                      contains a more detailed output of the NMR observables in a
                      MagresView-readable format. The following simulations are
                      included: $AlPO4_bulk$ The different bulk phases of
                      anhydrous AlPO4 (berlinite, cristobalite, tridymite
                      polymorphs) as well as AlPO4 hydrates (variscite, UiO-7).
                      $AlPO4_surface$ The different surface models for berlinite
                      AlPO4 as well as the convergence test for the 001 slab.
                      $AlPO4_surfaceH2O$ The different hydrated and hydroxylated
                      berlinite AlPO4 surface models based on the buckled
                      berlinite surface. $AlPO4_TMPES$ The isolated TMPES molecule
                      as well as the chemisorbed and physisorbed hydroxylated
                      TMPES on top of the (P-OH)2 surface of buckled berlinite
                      AlPO4.},
      cin          = {IET-1},
      cid          = {I:(DE-Juel1)IET-1-20110218},
      pnm          = {1223 - Batteries in Application (POF4-122) / DFG project
                      G:(GEPRIS)390776260 - EXC 2089: e-conversion (390776260) /
                      AdamBatt - Fortschrittliche Materialien für die Anwendung
                      in Hybriden Festkörperbatterien (13XP0305A) / HITEC -
                      Helmholtz Interdisciplinary Doctoral Training in Energy and
                      Climate Research (HITEC) (HITEC-20170406)},
      pid          = {G:(DE-HGF)POF4-1223 / G:(GEPRIS)390776260 /
                      G:(BMBF)13XP0305A / G:(DE-Juel1)HITEC-20170406},
      typ          = {PUB:(DE-HGF)32},
      doi          = {10.26165/JUELICH-DATA/MZPCAS},
      url          = {https://juser.fz-juelich.de/record/1046220},
}