Ilaria Ciofini

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The possibility of using vanadyl ions as paramagnetic biomarkers for the identification of traces of primitive life fossilized in silica rocks is studied by cw-EPR, ENDOR, HYSCORE, and DFT calculations. It is well-known that porphyrins, which are common to all living organisms, form vanadyl-porphyrin complexes in sediments deposited in oceans. However, the(More)
Since Antiquity, humans have produced and commercialized dyes. To this day, extraction of natural dyes often requires lengthy and costly procedures. In the 19th century, global markets and new industrial products drove a significant effort to synthesize artificial dyes, characterized by low production costs, huge quantities, and new optical properties(More)
We assessed the accuracy of the four members of the M06 family of functionals (M06-L, M06, M06-2X, and M06-HF) for the prediction of electronic excitation energies of main-group compounds by time-dependent density functional theory. This is accomplished by comparing the predictions both to high-level theoretical benchmark calculations and some experimental(More)
With the aim of understanding the elementary steps governing the oxidation of CO catalyzed by dispersed or supported gold nanoclusters, the adsorption of molecular species, such as O2 and CO, on model neutral and positively charged clusters (Au(n)(m+) n = 1, 9, and 13; m = 0, 1, and 3) has been studied using an ab initio approach. The computed structural(More)
The mechanism of the palladium-catalyzed homocoupling of arylboronic acids ArB(OH)(2) (Ar = 4-Z-C(6)H(4) with Z = MeO, H, CN) in the presence of dioxygen, leading to symmetrical biaryls, has been fully elucidated. The peroxo complex (eta(2)-O(2))PdL(2) (L = PPh(3)), generated in the reaction of dioxygen with the Pd(0) catalyst, was found to play a crucial(More)
The π → π* transitions of more than 100 organic dyes from the major classes of chromophores (quinones, diazo, ...) have been investigated using a Time-Dependent Density Functional Theory (TD-DFT) procedure relying on large atomic basis sets and the systematic modeling of solvent effects. These calculations have been performed with pure (PBE) as well as(More)
We assess the accuracy of eight Minnesota density functionals (M05 through M08-SO) and two others (PBE and PBE0) for the prediction of electronic excitation energies of a family of four cyanine dyes. We find that time-dependent density functional theory (TDDFT) with the five most recent of these functionals (from M06-HF through M08-SO) is able to predict(More)
Vibrationally resolved absorption spectra of a series of anthraquinoidic dyes have been obtained with a polarizable continuum model time-dependent density functional theory approach. Firstly, we assessed the impact of the atomic basis set on both the transition energies and the vibronic shapes of 1,4-NH2-anthraquinone using a large panel of Pople's basis(More)
With the aim of defining the spatial extent associated to an electronic transition, of particular relevance in the case of charge-transfer (CT) excitations, a new index, evaluated only from the computed density for the ground and excited state, is here derived and tested on a family of molecules that can be considered as prototypes of push-pull(More)
Ground-state (GS) and excited-state (ES) properties of novel photomagnetic molecular devices (PMMDs) are investigated by means of density functional theory. These organic PMMDs undergo a ferromagnetic alignment of their intramolecular spins in the lowest ES. They are comprised of: 1) an anthracene unit (An) as both the photosensitizer (P) and a transient(More)