Density Functional Theory (DFT) has had a major impact as a complementary tool for experimental inorganic chemists. The use DFT calculations allow to gain insight into the electronic structure of transition metal compounds and its implications in structure, reactivity and physical properties. In this communication we present our results for the application of the meta-hybrid GGA functional TPSSh1,2 for the accurate calculation of relative energies between different spin-states in transition metal complexes. Our methodology has been tested in the theoretical calculation of transition temperatures (T1/2) for the [Fe(stpy)4(NCX)2] (X= S, Se, BH3) family of spin-crossover systems with unprecedented accuracy. Fundamental insights into the dependence of T1/2 on the nature of the axial ligands are obtained from the direct analysis of the underlying electronic structure in terms of the relevant molecular orbitals.3 This methodology has also been applied to the study of the [Fe(TMP)CN]- anion to unravel the reasons for the thermally accessible high-spin state.4 The reported methodology can be used to get quantitative information in processes where the electronic structure of the metal center changes qualitatively and more than one spin state become relevant.           References:     (1)      Perdew, J. P.; Tao, J. M.; Staroverov, V. N.; Scuseria, G. E. Journal of Chemical Physics 2004, 120, 6898.  (2)      Tao, J. M.; Perdew, J. P.; Staroverov, V. N.; Scuseria, G. E. Physical Review Letters 2003, 91.  (3)      Cirera, J.; Paesani, F. Inorganic Chemistry 2012, 51, 8194.  (4)      Cirera, J.; Alvarez, S. Dalton Transactions 2013, 42, 7002.

Accurate calculation of relative energies between different spin states in coordination complexes using density functional methods

247th National Meeting (2014)

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