Simulating Two-Dimensional Electronic Spectra

Speaker: Professor Ivan Rivalta
Institute: University of Bologna
Country: Italy
Speaker Link:

Professor Ivan Rivalta

Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Bologna, Italy

Laboratoire de Chimie UMR 5182, École Normale Supérieure de Lyon, CNRS, UCBL, Lyon, France

Two-dimensional electronic spectroscopy (2DES) is a developing multidimensional technique based on ultrashort laser pulses used to track electronic transitions in complex systems with femtosecond spectral and time resolution. 2DES in the ultraviolet (2DUV) can be used to investigate structure, conformation dynamics, energy transfer, and chemical/photochemical reactivity in a wide range of systems in physical chemistry, energy sciences and biophysics. The interpretation of 2D electronic spectra is challenging and computational modeling is required to disentangle the congested information contained in the nonlinear optical response of the sample. In this presentation, the 2DES technique and its theoretical basis are introduced along with an illustration of the computational tools and protocols that we developed to perform first-principles simulations of 2DES spectra.[1] The methodology has been so far applied to the study of structure and dynamics of various biological systems, including proteic systems [2], organic fluorescent probes [3] and DNA/RNA nucleobases.[4] Wavefunctions methods have been used to reliably calculate the electronic properties of multichromophoric systems, and compared with time-dependent density functional theory methodologies, using hybrid QM/MM schemes and in conjunction with molecular dynamics techniques to assess environmental and conformational effects that shape the 2D electronic spectra [5].


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1. I. Rivalta, Nenov A., Cerullo G., Mukamel S. and Garavelli M. Int. J. Quantum Chem. 2014, 114, 85-93; Segarra-Marti J., Mukamel, S., Garavelli, M., Nenov, A. and Rivalta I. Top. Curr. Chem. 2018, 376, 24.

2. Nenov A., Mukamel S., Garavelli M. and Rivalta I. J. Chem. Theory Comput. 2015, 11, 3755-3771.

3. Nenov A., Giussani A., Fingerhut B. P., Rivalta I., Dumont E., Mukamel S. and Garavelli M. Phys. Chem. Chem. Phys. 2015, 46, 30925-30936.

4. Segarra-Marti J., Jaiswal V. K., Pepino A. J., Giussani A., Nenov A., Mukamel S., Garavelli M. and Rivalta I. Faraday Discuss. 2018, 207, 233-250.

5. Borrego Varillas R., Nenov A., Ganzer L., Oriana A., Manzoni C., Rivalta I., Mukamel S., Garavelli M., Cerullo G. Chem. Sci., 2019,10, 9907-9921; Segarra-Marti J., Segatta F., Mackenzie T.A., Nenov, A., Rivalta I., Bearpark M.J., Garavelli M. Faraday Discuss., 2020, 221, 219

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