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Title: Ab initio study of metal-organic framework-5 Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3}: An assessment of mechanical and spectroscopic properties

Abstract

The electronic structure of porous metal-organic framework-5 (MOF-5) of composition Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3} was investigated with an ab initio density-functional-theory method. The unit cell volume and atomic positions were optimized with the well-known local-density approximation leading to a good agreement between the experimental and theoretical equilibrium structural parameters. Single crystal elastic constants (C{sub 11}, C{sub 12}, and C{sub 44}) were then computed at the athermal limit in order to estimate fundamental figures for technological and engineering applications. Our calculations suggest that MOF-5 behaves as a soft and ductile material with a Young's modulus of the order of Oak wood. Particular attention was also focused on the study of oxygen, and carbon K XANES spectra. The differences in their shapes and energy peak positions were discussed in relation to the bonding topology and to the different calculational methods used.

Authors:
; ;  [1]
  1. Departamento de Fisica de la Materia Condensada, Universidad Autonoma de Madrid, E-28049 (Spain)
Publication Date:
OSTI Identifier:
20787952
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. B, Condensed Matter and Materials Physics; Journal Volume: 73; Journal Issue: 9; Other Information: DOI: 10.1103/PhysRevB.73.094111; (c) 2006 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ABSORPTION SPECTROSCOPY; APPROXIMATIONS; CARBON; DENSITY FUNCTIONAL METHOD; DUCTILITY; ELECTRONIC STRUCTURE; MONOCRYSTALS; ORGANOMETALLIC COMPOUNDS; OXYGEN; POROUS MATERIALS; X-RAY SPECTROSCOPY; YOUNG MODULUS; ZINC COMPOUNDS

Citation Formats

Mattesini, M., Soler, J. M., and Yndurain, F. Ab initio study of metal-organic framework-5 Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3}: An assessment of mechanical and spectroscopic properties. United States: N. p., 2006. Web. doi:10.1103/PHYSREVB.73.0.
Mattesini, M., Soler, J. M., & Yndurain, F. Ab initio study of metal-organic framework-5 Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3}: An assessment of mechanical and spectroscopic properties. United States. doi:10.1103/PHYSREVB.73.0.
Mattesini, M., Soler, J. M., and Yndurain, F. Wed . "Ab initio study of metal-organic framework-5 Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3}: An assessment of mechanical and spectroscopic properties". United States. doi:10.1103/PHYSREVB.73.0.
@article{osti_20787952,
title = {Ab initio study of metal-organic framework-5 Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3}: An assessment of mechanical and spectroscopic properties},
author = {Mattesini, M. and Soler, J. M. and Yndurain, F.},
abstractNote = {The electronic structure of porous metal-organic framework-5 (MOF-5) of composition Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3} was investigated with an ab initio density-functional-theory method. The unit cell volume and atomic positions were optimized with the well-known local-density approximation leading to a good agreement between the experimental and theoretical equilibrium structural parameters. Single crystal elastic constants (C{sub 11}, C{sub 12}, and C{sub 44}) were then computed at the athermal limit in order to estimate fundamental figures for technological and engineering applications. Our calculations suggest that MOF-5 behaves as a soft and ductile material with a Young's modulus of the order of Oak wood. Particular attention was also focused on the study of oxygen, and carbon K XANES spectra. The differences in their shapes and energy peak positions were discussed in relation to the bonding topology and to the different calculational methods used.},
doi = {10.1103/PHYSREVB.73.0},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 9,
volume = 73,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2006},
month = {Wed Mar 01 00:00:00 EST 2006}
}
  • Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less
  • We investigate the structure and ferroelectric behavior of a lanthanide based metal-organic framework (MOF), [Nd(C{sub 4}H{sub 5}O{sub 6})(C{sub 4}H{sub 4}O{sub 6})][3H{sub 2}O]. X-ray crystal structure analyses reveal that it crystallizes in the P4{sub 1}2{sub 1}2 space group with Nd centres, coordinated by nine oxygen atoms, forming a distorted capped square antiprismatic geometry. The molecules, bridged by tartrate ligands, form a 2D chiral structure. The 2D sheets are further linked into a 3D porous framework via strong hydrogen-bonding scheme (O-H…O ≈ 2.113 Å). Dielectric studies reveal two anomalies at 295 K and 185 K. The former is a paraelectric-ferroelectric transition, and the later is attributed tomore » the freezing down of the motion of the hydroxyl groups. The phase transition is of second order, and the spontaneous polarization in low temperature phase is attributed to the ordering of protons of hydroxyl groups. The dielectric nonlinearity parameters have been calculated using Landau– Devonshire phenomenological theory. In addition, the most recent semiempirical models, Sparkle/PM7, Sparkle/RM1, and Sparkle/AM1, are tested on the present system to assay the accuracy of semiempirical quantum approaches to predict the geometries of solid MOFs. Our results show that Sparkle/PM7 model is the most accurate to predict the unit cell structure and coordination polyhedron geometry. The semiempirical methods are also used to calculate different ground state molecular properties.« less
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