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Title: Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O and Co-O bonded interactions for tephroite, Mn 2SiO 4, fayalite, Fe 2SiO 4 and Co 2SiO 4 olivine and selected organic metal complexes: Comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides

Abstract

Bond critical point, bcp, and local energy density properties for the electron density, ED, distributions, calculated with first principle quantum mechanical methods for divalent transition metal Mn-, Co- and Fe-containing silicates and oxides are compared with experimental model ED properties for tephroite, Mn 2SiO 4, fayalite, Fe 2SiO 4 and Co 2SiO 4 olivine, each determined with high energy synchrotron single crystal X-ray diffraction data. Trends observed between the experimental bond lengths, R(M-O), (M = Mn, Fe, Co), and the calculated bcp properties are comparable with those observed for non-transition M-O bonded interactions. The bcp, local total energy density, H(r c), and bond length trends determined for the Mn-O, Co-O and Fe-O interactions are virtually identical. A comparison is also made with model experimental bcp properties determined for several Mn-O, Fe-O and Co-O bonded interactions for organometallic complexes and several oxides. Despite the complexities of the structures of the organometallic complexes, the agreement between the calculated and the model experimental bcp properties is good in several cases. The G(r c)/p(r c) vs. R(M-O) trends established for non-transition metal M-O bonded interactions hold for the given transition metal M O bonded interactions with the G(r c)/p(r c) ratio increasing in valuemore » as H(r c) becomes progressively more negative in value and the shared character of the interaction increases. As observed for the non-transition metal M-O bonded interactions, the Laplacian, (nabla) 2p(r c), increases in value as p(r c) increases and as H(r c) decreases. The Mn-O, Fe-O, and Co-O bonded interactions are indicated to be of intermediate character with a substantial component of closed-shell character compared with Fe-S and Ni-S bonded interactions which show greater shared character based on the |V(r c)|/G(r c) bond character indicator. The atomic charges conferred on the transition metal atoms for the three olivines decrease with increasing atomic number from Mn to Fe to Co.« less

Authors:
 [1];  [2];  [1];  [3];  [1];  [4];  [5];  [6];  [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Univ. of Arizona, Tucson, AZ (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Univ. of Bonn (Germany)
  5. GKSS, Geesthacht (Germany)
  6. HASYLAB/DESY, Hamburg (Germany)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
946632
Report Number(s):
PNNL-SA-60572
Journal ID: ISSN 1932-7447; 25629; KC0303020; TRN: US0900986
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 112; Journal Issue: 37
Country of Publication:
United States
Language:
English
Subject:
43 PARTICLE ACCELERATORS; ATOMIC NUMBER; ATOMS; BOND LENGTHS; ELECTRON DENSITY; ENERGY DENSITY; LAPLACIAN; MONOCRYSTALS; OLIVINE; OXIDES; SILICATES; SYNCHROTRONS; TRANSITION ELEMENTS; X-RAY DIFFRACTION; Electron density; olivine; silicate; oxide; transition metal; bonding; Environmental Molecular Sciences Laboratory

Citation Formats

Gibbs, Gerald V., Downs, R. T., Cox, David F., Rosso, Kevin M., Ross, Nancy L., Kirfel, Armin, Lippmann, Thomas, Morgenroth, W., and Crawford, T. Daniel. Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O and Co-O bonded interactions for tephroite, Mn2SiO4, fayalite, Fe2SiO4 and Co2SiO4 olivine and selected organic metal complexes: Comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides. United States: N. p., 2008. Web. doi:10.1021/jp804280j.
Gibbs, Gerald V., Downs, R. T., Cox, David F., Rosso, Kevin M., Ross, Nancy L., Kirfel, Armin, Lippmann, Thomas, Morgenroth, W., & Crawford, T. Daniel. Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O and Co-O bonded interactions for tephroite, Mn2SiO4, fayalite, Fe2SiO4 and Co2SiO4 olivine and selected organic metal complexes: Comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides. United States. doi:10.1021/jp804280j.
Gibbs, Gerald V., Downs, R. T., Cox, David F., Rosso, Kevin M., Ross, Nancy L., Kirfel, Armin, Lippmann, Thomas, Morgenroth, W., and Crawford, T. Daniel. Wed . "Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O and Co-O bonded interactions for tephroite, Mn2SiO4, fayalite, Fe2SiO4 and Co2SiO4 olivine and selected organic metal complexes: Comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides". United States. doi:10.1021/jp804280j.
@article{osti_946632,
title = {Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O and Co-O bonded interactions for tephroite, Mn2SiO4, fayalite, Fe2SiO4 and Co2SiO4 olivine and selected organic metal complexes: Comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides},
author = {Gibbs, Gerald V. and Downs, R. T. and Cox, David F. and Rosso, Kevin M. and Ross, Nancy L. and Kirfel, Armin and Lippmann, Thomas and Morgenroth, W. and Crawford, T. Daniel},
abstractNote = {Bond critical point, bcp, and local energy density properties for the electron density, ED, distributions, calculated with first principle quantum mechanical methods for divalent transition metal Mn-, Co- and Fe-containing silicates and oxides are compared with experimental model ED properties for tephroite, Mn2SiO4, fayalite, Fe2SiO4 and Co2SiO4 olivine, each determined with high energy synchrotron single crystal X-ray diffraction data. Trends observed between the experimental bond lengths, R(M-O), (M = Mn, Fe, Co), and the calculated bcp properties are comparable with those observed for non-transition M-O bonded interactions. The bcp, local total energy density, H(rc), and bond length trends determined for the Mn-O, Co-O and Fe-O interactions are virtually identical. A comparison is also made with model experimental bcp properties determined for several Mn-O, Fe-O and Co-O bonded interactions for organometallic complexes and several oxides. Despite the complexities of the structures of the organometallic complexes, the agreement between the calculated and the model experimental bcp properties is good in several cases. The G(rc)/p(rc) vs. R(M-O) trends established for non-transition metal M-O bonded interactions hold for the given transition metal M O bonded interactions with the G(rc)/p(rc) ratio increasing in value as H(rc) becomes progressively more negative in value and the shared character of the interaction increases. As observed for the non-transition metal M-O bonded interactions, the Laplacian, (nabla)2p(rc), increases in value as p(rc) increases and as H(rc) decreases. The Mn-O, Fe-O, and Co-O bonded interactions are indicated to be of intermediate character with a substantial component of closed-shell character compared with Fe-S and Ni-S bonded interactions which show greater shared character based on the |V(rc)|/G(rc) bond character indicator. The atomic charges conferred on the transition metal atoms for the three olivines decrease with increasing atomic number from Mn to Fe to Co.},
doi = {10.1021/jp804280j},
journal = {Journal of Physical Chemistry. C},
number = 37,
volume = 112,
place = {United States},
year = {Wed Aug 20 00:00:00 EDT 2008},
month = {Wed Aug 20 00:00:00 EDT 2008}
}