PRIN - FRONTIERS

2013 - 2016
Title: 
Frontier studies in molecular spectroscopy and dynamics: from simple molecular systems to supramolecular aggregates and advanced materials
Principal Investigator: 
Fabrizio Santoro
Project type: 
National
Labs: 
ThC2-Lab

Abstract

The national project is coordinated by Prof. W. Caminati (University of Bologna). Pisa Research Unit (RU) of the Project is settled at Consiglio Nazionale delle Ricerche and involves researchers with a theoretical and computational background affiliated to different Institutions. The broad expertise of Pisa RU provides support to the experimental studies performed in the Project. The work of Pisa RU will bridge methodological developments and frontiers applications in collaboration with the other RUs. Main focus will be the structural, spectroscopic and ground and excited dynamical effects of weak interactions like hydrogen and halogen bondings, stacking, and exciton couplings on systems and processes in line with Solar Energy, Advanced Materials and Space goals of Horizon 2020. Our project involves collaboration with national institutions (Uni-Pi and SNS-Pi) and top leading European research groups in Germany, France, Spain and Norway Pisa RU will develop models and computational tools for the investigation of optical properties and nonaradiative processes of electronically excited species. We will generalize the time-independent methods recently developed by us for the simulation of steady state optical spectra or large-size systems described within harmonic approximation, by including anharmonic energy profiles and implementing alternative time-dependent routes that solve the problems of convergence for very large systems. Furthermore, we will develop approaches to deal with the general nonadiabatic problem of the optical and photophysical properties of oligomers of dyes, taking into account exciton formation, and energy and charge-transfers. The main ingredients of our computational strategy will be vibronic models, hierarchical transformations of the Hamiltonian, to rigorously obtain few collective coordinates that reproduce the short-time nonadiabatic dynamics of the whole system, and quantum dynamical simulations through multiconfigurational approaches We also aim at simulating time-resolved spectra and two-dimensional optical spectroscopies. Applications will span from the study of decay dynamics in photoexcited DNA oligomers, to energy transfer in natural and artificial photosynthetic systems (with Firenze RU) and photophysical properties of chromophore in the solid state (with Parma RU).With Bologna, Milano and Perugia RUs we will study systems characterized by hydrogen and halogen bonds, to understand their structure, get insight into the physical nature of the interaction and evaluate its the strength. Simulation of the dynamics (hydrogen transfer) and spectroscopic signals will complete the analysis.Reactive scattering processes of atoms and small molecular species with surfaces will be investigated by molecular dynamics, according to semiclassical and mixed quantum/classical approaches (with Perugia RU). We aim at establishing correlations between reactivity and physical-chemical properties of chemical species andsolid substrates and at building up accurate database of scattering processes. Case studies will be O,O2,N,N2 on silica, dissociative chemisorptions of CH4 on zeolites, and recombination of hydrogen atoms on graphite.We will also study reactive scattering of elementary species for its potential in unraveling the details of fundamental processes, including those operating in the chemistry of early universe. We will focus on reactive pathways of LiH, LiH+ and HeH+molecules (with Perugia and Bari RUs). Simulations will be carried according to time-independent hyperspherical methodologies through codes developed by members of the RU. Numerical data will be analyzed through complex angular momentum techniques

People

  • Vincenzo Carravetta, IPCF-CNR, Pisa
  • Dario De Fazio, IMIP-CNR Montelibretti
  • Roberto Improta, IBB-CNR, Napoli
  • Alessndro Lami, ICCOM-CNR, Pisa
  • Maria Rutigliano, IMIP-CNR, Bari
  • Fabrizio Santoro, ICCOM-CNR, Pisa
  • Nico Sanna, CASPUR Roma