Exchange Interactions on the Highest-Spin Reported Molecule: the Mixed-Valence Fe42 Complex

被引：13
作者：
Aravena, Daniel [1 ]
Venegas-Yazigi, Diego [1 ,2 ]
Ruiz, Eliseo [3 ,4 ]
机构：
[1] Univ Santiago Chile USACH, Dept Quim Mat, Fac Quim & Biol, Santiago, Chile
[2] CEDENNA, Santiago, Chile
[3] Univ Barcelona, Dept Quim Inorganicai Organ, E-08028 Barcelona, Spain
[4] Inst Recerca Quim Teor & Computac, Barcelona 08028, Spain
来源：
SCIENTIFIC REPORTS | 2016年 / 6卷
关键词：
TRANSITION-METAL-COMPLEXES; DENSITY-FUNCTIONAL THEORY; COUPLING-CONSTANTS; GROUND-STATE; MAGNETIC-PROPERTIES; PRUSSIAN BLUE; ANISOTROPY; CLUSTER; MN-19; SYMMETRY;
D O I：
10.1038/srep23847
中图分类号：
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号：
07 ; 0710 ; 09 ;
摘要：
The finding of high-spin molecules that could behave as conventional magnets has been one of the main challenges in Molecular Magnetism. Here, the exchange interactions, present in the highest-spin molecule published in the literature, Fe-42, have been analysed using theoretical methods based on Density Functional Theory. The system with a total spin value S = 45 is formed by 42 iron centres containing 18 high-spin Fe-III ferromagnetically coupled and 24 diamagnetic low-spin Fe-II ions. The bridging ligands between the two paramagnetic centres are two cyanide ligands coordinated to the diamagnetic Fe-II cations. Calculations were performed using either small Fe-4 or Fe-3 models or the whole Fe-42 complex, showing the presence of two different ferromagnetic couplings between the paramagnetic Fe-III centres. Finally, Quantum Monte Carlo simulations for the whole system were carried out in order to compare the experimental and simulated magnetic susceptibility curves from the calculated exchange coupling constants with the experimental one. This comparison allows for the evaluation of the accuracy of different exchange-correlation functionals to reproduce such magnetic properties.
引用
收藏
页数：7
相关论文
共 49 条
[1]   A ferromagnetically coupled Mn19 aggregate with a record S=83/2 ground spin state [J].
Ako, Ayuk M. ;
Hewitt, Ian J. ;
Mereacre, Valeritt ;
Clerac, Rodolphe ;
Wernsdorfer, Wolfgang ;
Anson, Christopher E. ;
Powell, Annie K. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (30) :4926-4929
[2]  
Aromi G., 2012, MOL CLUSTER MAGNETS
[3]   Synthesis of 3d metallic single-molecule magnets [J].
Aromi, Guillem ;
Brechin, Euan K. .
SINGLE-MOLECULE MAGNETS AND RELATED PHENOMENA, 2006, 122 :1-67
[4]   The Drosophila of single-molecule magnetism: [Mn12O12(O2CR)16(H2O)4] [J].
Bagai, Rashmi ;
Christou, George .
CHEMICAL SOCIETY REVIEWS, 2009, 38 (04) :1011-1026
[5]   The ALPS project release 2.0: open source software for strongly correlated systems [J].
Bauer, B. ;
Carr, L. D. ;
Evertz, H. G. ;
Feiguin, A. ;
Freire, J. ;
Fuchs, S. ;
Gamper, L. ;
Gukelberger, J. ;
Gull, E. ;
Guertler, S. ;
Hehn, A. ;
Igarashi, R. ;
Isakov, S. V. ;
Koop, D. ;
Ma, P. N. ;
Mates, P. ;
Matsuo, H. ;
Parcollet, O. ;
Pawlowski, G. ;
Picon, J. D. ;
Pollet, L. ;
Santos, E. ;
Scarola, V. W. ;
Schollwoeck, U. ;
Silva, C. ;
Surer, B. ;
Todo, S. ;
Trebst, S. ;
Troyer, M. ;
Wall, M. L. ;
Werner, P. ;
Wessel, S. .
JOURNAL OF STATISTICAL MECHANICS-THEORY AND EXPERIMENT, 2011,
[6]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[7]   Ab initio molecular simulations with numeric atom-centered orbitals [J].
Blum, Volker ;
Gehrke, Ralf ;
Hanke, Felix ;
Havu, Paula ;
Havu, Ville ;
Ren, Xinguo ;
Reuter, Karsten ;
Scheffler, Matthias .
COMPUTER PHYSICS COMMUNICATIONS, 2009, 180 (11) :2175-2196
[8]   Spin density distribution in transition metal complexes: Some thoughts and hints [J].
Cano, J ;
Ruiz, E ;
Alvarez, S ;
Verdaguer, M .
COMMENTS ON INORGANIC CHEMISTRY, 1998, 20 (01) :27-56
[9]   Magnetic Properties of Largest-Spin Single Molecule Magnets: Mn17 Complexes-A Density Functional Theory Approach [J].
Cremades, Eduard ;
Ruiz, Eliseo .
INORGANIC CHEMISTRY, 2010, 49 (20) :9641-9648
[10]   VALENCE DELOCALIZATION IN PRUSSIAN BLUE FE4III[FEII(CN)6]3.XD2O, BY POLARIZED NEUTRON-DIFFRACTION [J].
DAY, P ;
HERREN, F ;
LUDI, A ;
GUDEL, HU ;
HULLIGER, F ;
GIVORD, D .
HELVETICA CHIMICA ACTA, 1980, 63 (01) :148-153
12345