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Title: H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations: H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations

Abstract

We report neutron-diffraction investigations of the quasi-2D Mn-II(dca)(2)(pym)(H2O) (pym = N2C4H4) compound, where high-spin Mn-II ions are bridged by dicyanamide anions, [N(CN)(2)](-) (herein abbreviated dca). Inside the layers, Mn2+ ions are connected by single or double dca bridges. The magnetic phase diagram was established by neutron diffraction on a single crystal. In the low-field phase, the Mn-II ions are antiferro-magnetically ordered in the layers, with moments nearly parallel to the c axis, and the layers are antiferromagnetically coupled. The spin-flop phase corresponds to ferromagnetic coupling between the antiferromagnetic layers, in which the Mn-II moments are nearly perpendicular to the c axis. The induced spin-density distribution in the paramagnetic phase, determined by polarized neutron diffraction, visualizes the super-exchange pathways through the dca ligands within the layers and through H bonding between neighboring layers. The theoretical spin density obtained by bidimensional periodic DFT calculations is compared with the experimental results. Furthermore, quantum Monte Carlo simulations have been performed to compare the DFT results with experimental susceptibility measurements.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2];  [3];  [4]; ORCiD logo [5]
  1. Laboratoire Léon Brillouin (LLB), CEA-CNRS, CE Saclay 91191 Gif-sur-Yvette Cedex France
  2. Laboratoire MOLTECH-Anjou, Université d'Angers, CNRS UMR, 6200, 2 bd Lavoisier 49045 Angers Cedex France
  3. Departament de Química Inorgànica i Orgànica and Institut de Química Teòrica i Computacional, Universitat de Barcelona, Diagonal 645 08028 Barcelona Spain
  4. Materials Science Division, Argonne National Laboratory, Bldg. 200, 9700 S. Cass Avenue 60439 Argonne IL USA
  5. Department of Chemistry, Biochemistry and Physics, Eastern Washington University, 99004 Cheney WA USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Spanish Ministerio de Economia y Competitividad (MINECO)
OSTI Identifier:
1461305
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2018; Journal Issue: 3-4; Journal ID: ISSN 1434-1948
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
density functional calculations; dicyanamides; exchange coupling; magnetic properties; transition metals

Citation Formats

Gillon, Béatrice, Hammerschmied, Albert, Gukasov, Arsen, Cousson, Alain, Cauchy, Thomas, Ruiz, Eliseo, Schlueter, John A., and Manson, Jamie L. H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations: H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations. United States: N. p., 2017. Web. doi:10.1002/ejic.201700971.
Gillon, Béatrice, Hammerschmied, Albert, Gukasov, Arsen, Cousson, Alain, Cauchy, Thomas, Ruiz, Eliseo, Schlueter, John A., & Manson, Jamie L. H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations: H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations. United States. doi:10.1002/ejic.201700971.
Gillon, Béatrice, Hammerschmied, Albert, Gukasov, Arsen, Cousson, Alain, Cauchy, Thomas, Ruiz, Eliseo, Schlueter, John A., and Manson, Jamie L. Wed . "H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations: H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations". United States. doi:10.1002/ejic.201700971.
@article{osti_1461305,
title = {H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations: H-Mediated Magnetic Interactions between Layers in a 2D Mn II -Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations},
author = {Gillon, Béatrice and Hammerschmied, Albert and Gukasov, Arsen and Cousson, Alain and Cauchy, Thomas and Ruiz, Eliseo and Schlueter, John A. and Manson, Jamie L.},
abstractNote = {We report neutron-diffraction investigations of the quasi-2D Mn-II(dca)(2)(pym)(H2O) (pym = N2C4H4) compound, where high-spin Mn-II ions are bridged by dicyanamide anions, [N(CN)(2)](-) (herein abbreviated dca). Inside the layers, Mn2+ ions are connected by single or double dca bridges. The magnetic phase diagram was established by neutron diffraction on a single crystal. In the low-field phase, the Mn-II ions are antiferro-magnetically ordered in the layers, with moments nearly parallel to the c axis, and the layers are antiferromagnetically coupled. The spin-flop phase corresponds to ferromagnetic coupling between the antiferromagnetic layers, in which the Mn-II moments are nearly perpendicular to the c axis. The induced spin-density distribution in the paramagnetic phase, determined by polarized neutron diffraction, visualizes the super-exchange pathways through the dca ligands within the layers and through H bonding between neighboring layers. The theoretical spin density obtained by bidimensional periodic DFT calculations is compared with the experimental results. Furthermore, quantum Monte Carlo simulations have been performed to compare the DFT results with experimental susceptibility measurements.},
doi = {10.1002/ejic.201700971},
journal = {European Journal of Inorganic Chemistry},
issn = {1434-1948},
number = 3-4,
volume = 2018,
place = {United States},
year = {2017},
month = {11}
}

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