Contacts:
Supervisor(s):
Prof. Giovanni Granucci, prof.ssa Benedetta Mennucci
Title of the PhD project:
Development of multi-scale approaches for photochemical processes in complex environments.
Abstract of the PhD project:
Nonadiabatic phenomena are relevant in many photophysical and photochemical processes, including some fundamental biochemical phenomena such as photosynthesis and photoreception and DNA photodamage. Moreover, nonadiabatic processes are at the basis of important therapeutic strategies such as the photodynamic therapy (PDT), a promising type of cancer treatment that uses a photosensitizer (PS), which accumulates in the target cell and, after exposure to the specific type of light, produces reactive singlet oxygen to kill the cell.
One of the approaches to study this kind of phenomena is based on the classical description of nuclei and on a quantum-mechanical description of electrons, that is the Surface Hopping method, with electronic energies and couplings evaluated on the fly in a semiempirical framework using the Floating Occupation Molecular Orbitals-Configurations Interaction (FOMO-CI) approach. In the FOMO-CI method the occupation numbers of the orbitals belonging to the active space are left free to float and the electronic wavefunction is evaluated in a CI scheme. In order to perform a geometry optimization or a molecular dynamics simulation with this approach it is necessary to develop a method for calculation of analytical gradients of the molecular energy with respect to the nuclear coordinates.
My doctoral work will focus on an implementation and an application part. The former consists in implementing the FOMO and, consequently, the surface hopping nonadiabatic dynamics in the Gaussian 16 package, also to couple it with a polarizable embedding, in order to study biological systems in complex environments. With this method I will investigate and characterize molecules used in PDT to evaluate their potential as PSs, as well as the interaction of the singlet oxygen with a PS, and also, I will study the photochemistry involved in photoresponsive proteins such as the class of phytochromes.
Publications:
• Dye Stabilization and Wavelength Tunability in Lasing Fibers Based on DNA, Advanced Optical Materials 2020; 2001039.
• Elucidating the role of structural fluctuations, intermolecular and vibronic interactions in the spectroscopic response of a bacteriophytochrome, Phys. Chem. Chem. Phys. 2020; 22: 8585;
• Binding of model polycyclic aromatic hydrocarbons and carbamate-pesticides to DNA, BSA, micelles and liposomes, Spectrochim Acta A Mol Biomol Spectrosc. 2019; 223: 117313
Oral communications at conferences:
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Poster communications at conferences:
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Other achievements:
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