Cooperativity of Spin Crossover Complexes: Combining Periodic Density Functional Calculations and Monte Carlo Simulations

被引:8
|
作者
Kreutzburg, Lars [1 ]
Huebner, Christian G. [1 ]
Paulsen, Hauke [1 ]
机构
[1] Univ Lubeck, Inst Phys, Ratzeburger Allee 160, D-23562 Lubeck, Germany
关键词
spin crossover; density functional calculations; Hubbard model; solid state; Slichter-Drickamer model; Monte Carlo simulation; Ising model; 71; 15; Mb; 75; 10; Hk; 30; Wx; METAL-ORGANIC FRAMEWORK; ISING-LIKE MODEL; VIBRATIONAL-SPECTRA; TRANSITION; STATE; FE(PHEN)2(NCS)2;
D O I
10.3390/ma10020172
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The total enthalpies of the 16 different spin configurations that can be realized in the unit cell of the archetype spin crossover complex [Fe(phen)(2)(NCS)(2)] (phen = 1,2-phenanthroline) were calculated, applying periodic density functional theory combined with the Hubbard model and the Grimme-D2 dispersion correction (DFT+U+D2). The obtained enthalpy differences between the individual spin configurations were used to determine spin couplings of an Ising-like model, and subsequent Monte Carlo simulations for this model allowed the estimation of the phenomenological interaction parameter Gamma of the Slichter-Drickamer model, which is commonly used to describe the cooperativity of the spin transition. The calculation procedure described herewhich led to an estimate of about 3 kJ center dot mol(-1) for Gamma, in good agreement with experimentmay be used to predict from first principles how modifications of spin crossover complexes can change the character of the spin transition from gradual to abrupt and vice versa.
引用
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页数:11
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