Naslov
Thermochemistry of spin-crossover Fe(II)complexes calculated with density functional methods

Autori
Baranović, Goran

Izvornik
Chemical physics letters (0009-2614) 369 (2003); 668-672

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
spin-crossover; density functional; thermochemistry

Sažetak
The geometries and vibrational frequencies of an iron(II) spin-crossover complex Fe(phen)2(NCS)2 in the low- and high-spin state have been calculated using DFT (BP86 functional with 6-31G* and LANL2DZ basis sets). A redundancy-free set of internal coordinates has been defined and used to obtain a valence force field. The use of the symmetry coordinates of a perfect octahedron as internal coordinates for the FeN6 framework of the complex has enabled the description of the stretching-bending couplings. A comparison of the force constants of free ligands with the corresponding constants of the two spin states has served as (provided / established) a basis for the discussion of the changes in electronic charge distribution in the complex. By use of the generalized harmonic mode scrambling it is shown that in the low-lying normal vibrations of the complex, the ligands participate as almost rigid units. Energies of tThese modes are in energy close to the oscillators describing the interaction of the complex with the surrounding molecules in the solid phase.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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