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Title: Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

Abstract

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M{sub 13}. First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first-principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M{sub 13} structures. Several new lower energy configurations were identified, e.g., Pd{sub 13}, W{sub 13}, Pt{sub 13}, etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and doublemore » simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au{sub 13}, we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.« less

Authors:
;
Publication Date:
OSTI Identifier:
21366731
Resource Type:
Journal Article
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Volume: 81; Journal Issue: 15; Other Information: DOI: 10.1103/PhysRevB.81.155446; (c) 2010 The American Physical Society; Journal ID: ISSN 1098-0121
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 36 MATERIALS SCIENCE; ATOMIC CLUSTERS; BINDING ENERGY; BOND LENGTHS; COORDINATION NUMBER; D STATES; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; EXCHANGE INTERACTIONS; LAYERS; L-S COUPLING; MAGNETIC PROPERTIES; METALS; MOLECULAR DYNAMICS METHOD; NANOSTRUCTURES; SIMULATION; SURFACES; THREE-DIMENSIONAL CALCULATIONS; TWO-DIMENSIONAL CALCULATIONS; CALCULATION METHODS; COUPLING; DIMENSIONS; ELEMENTS; ENERGY; ENERGY LEVELS; INTERACTIONS; INTERMEDIATE COUPLING; LENGTH; PHYSICAL PROPERTIES; VARIATIONAL METHODS

Citation Formats

Piotrowski, Mauricio J, Piquini, Paulo, Da Silva, Juarez L. F., and Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Cx. Postal 369, Sao Carlos 13560-970, SP. Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters. United States: N. p., 2010. Web. doi:10.1103/PHYSREVB.81.155446.
Piotrowski, Mauricio J, Piquini, Paulo, Da Silva, Juarez L. F., & Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Cx. Postal 369, Sao Carlos 13560-970, SP. Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters. United States. https://doi.org/10.1103/PHYSREVB.81.155446
Piotrowski, Mauricio J, Piquini, Paulo, Da Silva, Juarez L. F., and Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Cx. Postal 369, Sao Carlos 13560-970, SP. 2010. "Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters". United States. https://doi.org/10.1103/PHYSREVB.81.155446.
@article{osti_21366731,
title = {Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters},
author = {Piotrowski, Mauricio J and Piquini, Paulo and Da Silva, Juarez L. F. and Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Cx. Postal 369, Sao Carlos 13560-970, SP},
abstractNote = {The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M{sub 13}. First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first-principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M{sub 13} structures. Several new lower energy configurations were identified, e.g., Pd{sub 13}, W{sub 13}, Pt{sub 13}, etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au{sub 13}, we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.},
doi = {10.1103/PHYSREVB.81.155446},
url = {https://www.osti.gov/biblio/21366731}, journal = {Physical Review. B, Condensed Matter and Materials Physics},
issn = {1098-0121},
number = 15,
volume = 81,
place = {United States},
year = {Thu Apr 15 00:00:00 EDT 2010},
month = {Thu Apr 15 00:00:00 EDT 2010}
}