The gas phase structures of anisole dimer in the ground and first singlet electronic excited states have been characterized by a combined experimental and computational study. The dimer, formed in a molecular beam, has been studied by resonance-enhanced multiphoton ionization and high-resolution laser-induced fluorescence techniques. The assignment of the rotational fine structure of the S(1) <-- S(0) electronic transition origin has provided important structural information on the parallel orientation of aromatic rings of anisole moieties. By comparison with the DFT/TD-DFT computational results, it has been possible to infer the detailed equilibrium structure of the complex. The analysis of the equilibrium structure and interaction energy confirms that the anisole dimer is stabilized by dispersive interaction in the gas phase. This is, to the best of our knowledge, the first detailed work (reporting both theoretical and high-resolution experimental data) on an isolated cluster in the pi-stacking configuration.

An experimental and theoretical study is made on the anisole-water complex. It is the first van der Waals complex studied by high resolution electronic spectroscopy in which the water is seen acting as an acid. Vibronically and rotationally resolved electronic spectroscopy experiments and molecular mechanics calculations are used to elucidate the structure of the complex in the ground and first electronic excited state. Some internal dynamics in the system is revealed by high resolution spectroscopy.

In this paper, we report on the absorption, emission, and photodynamics of a push−pull zinc porphyrin (YD2-o-C8) in solution and adsorbed on Al 2 O 3 (alumina) nanoparticles (NPs). The shift in the absorption and emission spectra for the dye adsorbed on alumina NPs with respect to the solution suggests the presence of an anchoring effect of the dye to the NPs' surface. Indeed, different molecular populations (monomers and aggregates) coexist for the solid film, as it is confirmed by both steady-state and timeresolved measurements. The emission decays, while monoexponential in acetonitrile (ACN) solution (τ = 1.5 ns) become multiexponential (140 and 550 ps) for the dye interacting with the alumina NPs. These lifetime values increase (210 and 930 ps) upon addition of CDCA (a disaggregating agent). The deactivation (vibrational cooling) of the hot S 1 to cold S 1 state, which occurs in 4−6 ps in ACN, shows a biexponential behavior in the solid state (2 ps, 20 ps). These two ps components, whose values upon excitation at 460 nm do not change with respect to those observed without CDCA, become longer in the presence of the coadsorbent and exciting at 640 nm (4 ps, 50−60 ps), where the aggregates mostly absorb. The charge separation (2 ps in ACN, 15 ps in toluene) becomes faster in the solid state in absence of CDCA (∼500 and 110 fs exciting at 460 and 640 nm, respectively), while, by adding the coadsorbent, the process occurs on a time scale that is below our time-resolution (<50 fs). The obtained results are of potential interest to understand the dynamics of the porphyrin used in the up-to-now world-record-efficient dye-sensitized solar cell (DSSC).

State-of-the-art spectroscopic and theoretical methods have been exploited in a joint effort to elucidate the subtle features of the structure and the energetics of the anisole-ammonia 1:1 complex, a prototype of microsolvation processes. Resonance enhanced multiphoton ionization and laser-induced fluorescence spectra are discussed and compared to high-level first-principles theoretical models, based on density functional, many body second order perturbation, and coupled cluster theories. In the most stable nonplanar structure of the complex, the ammonia interacts with the delocalized pi electron density of the anisole ring: hydrogen bonding and dispersive forces provide a comparable stabilization energy in the ground state, whereas in the excited state the dispersion term is negligible because of electron density transfer from the oxygen to the aromatic ring. Ground and excited state geometrical parameters deduced from experimental data and computed by quantum mechanical methods are in very good agreement and allow us to unambiguously determine the molecular structure of the anisole-ammonia complex.