Latest Publications

Chemical Science 2017, 8, 4978-4986

DOI: 10.1039/C6SC05624E

Light Induced Excited Spin State Trapping (LIESST) in FeII spin-crossover systems is a process switching molecules from low (LS, S=0) to high spin (HS, S=2) states. The direct LS-to-HS conversion being forbidden by selection rules, LIESST involves intermediate states such as 1,3MLCT or 1,3T. The intersystem crossing sequence results in a HS state, structurally trapped by metal-ligand bond elongation through the coherent activation and damping of molecular breathing. The ultrafast dynamics of this process was so far investigated in FeN6 ligand field systems, under MLCT excitation. Here we study LIESST in an FeIIN4O2 spin-crossover material of lower symmetry, which allows quite intense and low-energy shifted d-d bands. By combining ab-initio DFT and TD-DFT calculations and fs optical absorption measurements we demonstrate that, compared to MLCT, d-d excitation induces faster LS-to-HS switching and that the shorter intermediates en...

Journal of Computational Chemistry 2017, 38 (14), 1084-1092

DOI: 10.1002/jcc.24780

The performances, in the description of excited state potential energy surfaces, of several density functional approximations representative of the currently most applied exchange correlation functionals’ families have been tested with respect to post Hartree-Fock references (here Symmetry Adapted Cluster-Configuration Interaction results). An experimentally well-characterized intermolecular proton transfer reaction has been considered as test case. The computed potential energy profiles were analyzed both in the gas phase and in toluene solution, here represented as a polarizable continuum model. The presence of intermolecular (dark) and intramolecular (bright) charge transfer excited states, whose polarity strongly differs along the reaction pathway, makes clear that only subtle compensation between spurious electronic effects—related to the incorrect asymptotic behavior of the functional—and solvent sta...

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