DFT calculations on the spin-crossover complex Fe(salen)(NO): a quest for the best functional

被引：171

作者：

Conradie, Jeanet

Ghosh, Abhik ^{[1
]}

机构：

[1] Univ Tromso, Dept Chem, Ctr Theoret & Computat Chem, N-9037 Tromso, Norway

[2] Univ Orange Free State, Dept Chem, ZA-9300 Bloemfontein, South Africa

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2007年 / 111卷 / 44期

关键词：

D O I：

10.1021/jp074480t

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：

DFT calculations on the spin-crossover complex Fe(salen)(NO) provide a striking illustration of the comparative performance of different exchange-correlation functionals vis-a-vis the issue of transition metal spin state energetics. Thus, although the "classic" pure functionals PW91 and BLYP favor the S = 1/2 state by about 10 kcal/mol, relative to the S = 3/2 state, the hybrid functional B3LYP favors the latter state by nearly the same margin. In contrast, the newer pure functionals OLYP and OPBE, based on the OPTX exchange functional, as well as the B3LYP* hybrid functional (which has 15% Hartree-Fock exchange, compared with 20% for B3LYP) predict nearly isoenergetic S = 1/2 and 3/2 states, as required for a spin-crossover complex. Intriguingly, the OLYP and B3LYP* spin density profiles for the S = 1/2 state of Fe(salen)(NO) are substantially dissimilar.

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页码：12621 / 12624

页数：4

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