Greta Donati

Absorption and emission spectral shapes of a prototype dye in water by combining classical/dynamical and quantum/static approaches.

We study the absorption and emission electronic spectra in an aqueous solution of N-methyl-6-oxyquinolinium betaine (MQ), an interesting dye characterized by a large change of polarity and H-bond ability between the ground (S0) and the excited (S1) states. To that end we compare alternative approaches based either on explicit solvent models and density functional theory (DFT)/molecular-mechanics (MM) calculations or on DFT calculations on clusters models embedded in a polarizable continuum (PCM). In the first approach (ClMD), the spectrum is computed according to the classical Franck-Condon principle, from the dispersion of the time-dependent (TD)-DFT vertical transitions at selected snapshots of molecular dynamics (MD) on the initial state. In the cluster model (Qst) the spectrum is simulated by computing the quantum vibronic structure, estimating the inhomogeneous broadening from state-specific TD-DFT/PCM solvent reorganization energies. While both approaches provide absorption and emission spectral shapes in nice agreement with experiment, the Stokes shift is perfectly reproduced by Qst calculations if S0 and S1 clusters are selected on the grounds of the MD trajectory. Furthermore, Qst spectra better fit the experimental line shape, mostly in absorption. Comparison of the predictions of the two approaches is very instructive: the positions of Qst and ClMD spectra are shifted due to the different solvent models and the ClMD spectra are narrower than the Qst ones, because MD underestimates the width of the vibrational density of states of the high-frequency modes coupled to the electronic transition. On the other hand, both Qst and ClMD approaches highlight that the solvent has multiple and potentially opposite effects on the spectral width, so that the broadening due to solute-solvent vibrations and electrostatic interaction with bulk solvent is (partially) counterbalanced by a narrowing of the contribution due to the solute vibrational modes. Qst analysis evidences a pure quantum broadening effect of the spectra in water due to vibronic progressions along the solute/solvent H-bonds.

Understanding THz and IR Signals beneath Time-Resolved Fluorescence from Excited-State Ab Initio Dynamics

The detailed interpretation of time-resolved spectroscopic signals in terms of the molecular rearrangement during a photoreaction or a photophysical event is one of the most important challenges of both experimental and theoretical chemistry. Here we simulate a time-resolved fluorescence spectrum of a dye in aqueous solution, the N-methyl-6-oxyquinolinium betaine, and analyze it in terms of far IR and THz frequency contributions, providing a direct connection to specific molecular motions. To obtain this result, we build up an innovative and general approach based on excited state ab-initio molecular dynamics and a wavelet-based time-dependent frequency analysis of nonstationary signals. We obtain a nice agreement with key parameters of the solvent dynamics, such as the total Stokes shift and the Stokes shift relaxation times. As an important finding, we observe a strong change of specific solute-solvent interactions upon the electronic excitation, with the migration of about 1.5 water molecules from the first solvation shell toward the bulk. In spite of this event, the Stokes shift dynamics is ruled by collective solvent motions in the THz and far IR, which guide and modulate the strong rearrangement of the dye microsolvation. By the relaxation of THz and IR contributions to the emission signal, we can follow and understand in detail the molecularity of the process. The protocol presented here is, in principle, transferable to other time-resolved spectroscopic techniques.

“Watching” Polaron Pair Formation from First-Principles Electron–Nuclear Dynamics

The formation of polaron pairs is one of the important photophysical processes that take place after the excitation in semiconducting organic polymers. First-principles Ehrenfest excited-state dynamics is a unique tool to investigate ultrafast photoinduced charge carrier dynamics and related nonequilibrium processes involving correlated electron-nuclear dynamics. In this work the formation of polaron pairs and their dynamical evolution in an oligomer of seven thiophene units is investigated with a combined approach of first-principles exciton-nuclear dynamics and wavelet analysis. The real-time formation of a polaron pair can be observed in the dipole evolution during the excited-state dynamics. The possible driving force of the polaron pair formation is investigated through qualitative correlation between the structural dynamics and the dipole evolution. The time-dependent characteristics and spectroscopic consequences of the polaron pair formation are probed using the wavelet analysis.

On the different strength of photoacids

AbstractIn spite of the detailed information provided by advanced time-resolved spectroscopy, the understanding of the excited-state proton transfer (ESPT) reactivity remains difficult to obtain at molecular level. In this work we studied three photoacids showing different strength: the 8-hydroxy-1,3,6-pyrenetrisulfonate weak photoacid, the N-methyl-6-hydroxyquinolinium strong photoacid and the phenol-carboxyether dipicolinium cyanine (QCy9) superphotoacid, focusing on the intermolecular ESPT toward a solvent molecule or a base molecule in aqueous solution. To this aim, the ground and the first singlet excited-state potential energy surfaces of the three systems were characterized by means of the time-dependent density functional theory and a hybrid implicit/explicit model of the solvent. Main structural and photophysical features of the photoacids were assessed and satisfactorily compared with the experimental data. Energy profiles along the PT coordinate were analyzed in both the electronic states. We reproduced many important features of the photoacidity experimentally observed. The results suggest that the relative strength is mainly due to the different extent of charge transfer caused by the electronic transition in proximity of the acid group. Remarkably, we found that even in the case of the strongest photoacid (QCy9), showing a ESPT rate as rapid as to escape the solvent dynamics control, the PT is modulated and supported by the first solvation shell of the proton-accepting molecule. However, a complete understanding of this fascinating field needs the full account for the electronic and the molecular dynamics in play at different timescales.

Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field

Real-time time-dependent density functional theory (RT-TDDFT) is a powerful tool for obtaining spectroscopic observables and understanding complex, time-dependent properties. Currently, performing RT-TDDFT calculations on large, fully quantum mechanical systems is not computationally feasible. Previously, polarizable mixed quantum mechanical and molecular mechanical (QM/MMPol) models have been successful in providing accurate, yet efficient, approximations to a fully quantum mechanical system. Here we develop a coupling scheme between induced dipole based QM/MMPol and RT-TDDFT. Our approach is validated by comparing calculated spectra with both real-time and linear-response TDDFT calculations. The model developed within provides an accurate method for performing RT-TDDFT calculations on extended systems while accounting for mutual polarization between the quantum mechanical and molecular mechanical regions.

Turn-on fluorescence detection of protein by molecularly imprinted hydrogels based on supramolecular assembly of peptide multi-functional blocks

Synthetic receptors for biomacromolecules lack the supramolecular self-assembly behavior typical of biological systems. Here we propose a new method for the preparation of protein imprinted polymers based on the specific interaction of a peptide multi-functional block with a protein target. This peptide block contains a protein-binding peptide domain, a polymerizable moiety at the C-terminus and an environment-sensitive fluorescent molecule at the N-terminus. The method relies on a preliminary step consisting of peptide/protein supramolecular assembly, followed by copolymerization with the most common acrylate monomers (acrylamide, acrylic acid and bis-acrylamide) to produce a protein imprinted hydrogel polymer. Such a peptide block can function as an active assistant recognition element to improve affinity, and guarantees its effective polymerization at the protein/cavity interface, allowing for proper placement of a dye. As a proof of concept, we chose Bovine Serum Albumin (BSA) as the protein target and built the peptide block around a BSA binding dodecapeptide, with an allyl group as the polymerizable moiety and a dansyl molecule as the responsive dye. Compared to conventional approaches these hydrogels showed higher affinity (more than 45%) and imprinted sensitivity (about twenty fold) to the target, with a great BSA selectivity with respect to ovalbumin (α = 1.25) and lysozyme (α = 6.02). Upon protein binding, computational and experimental observations showed a blue shift of the emission peak (down to 440 nm) and an increase of fluorescence emission (twofold) and average lifetime (Δτ = 4.3 ns). Such an approach generates recognition cavities with controlled chemical information and represents an a priori method for self-responsive materials. Provided a specific peptide and minimal optimization conditions are used, such a method could be easily implemented for any protein target.