Time-dependent photoinduced processes in isolated molecules and plasmonic systems.

by Ms Giulia Dall’Osto (Elettra Sincrotrone Trieste,)

Friday 27 Feb 2026, 10:00 → 11:00 Europe/Zurich

OVGA/200

Light–matter interactions provide fundamental insight into molecular properties, mediate chemical reactivity, and govern collective phenomena such as plasmon generation in metals. Among the theoretical strategies developed to describe these processes, time-dependent approaches based on ab initio wavefunction propagation via time-dependent Schrödinger equation (TDSE) are capable to model molecular interactions with one or multiple explicit electromagnetic pulses.1 Extending the closed-system TDSE to the stochastic Schrödinger equation2 within open quantum system theory enables inclusion of environmental effects, such as vibrational relaxation and decoherence, through appropriate dissipative operators.3 This framework is particularly suited for simulating ultrafast spectroscopic responses, where pulse durations reach the femtosecond regime, and for modeling time-resolved techniques. Applications include nonlinear spectroscopies (pump–probe, Raman,4 and 2D electronic spectroscopy5), chiroptical responses such as circular dichroism6 and circularly polarized luminescence, and time-resolved core spectroscopies, including NEXAFS. 
Furthermore, light-driven processes can be strongly mediated by plasmonic systems, motivating the investigation of plasmon generation in metal nanostructures under external electromagnetic fields. To describe extended systems such as metal nanoparticles, I employ the polarizable continuum model reformulated within the boundary element method.7 This approach captures the electromagnetic response of nanoparticles and the associated enhancement of external fields, whether molecular signals or laser pulses.8,9 Within a multiscale framework combining a quantum description of the molecule with a classical treatment of the metal substrate, this methodology has been successfully applied to the simulation of various plasmon-mediated phenomena. Both time- and frequency-domain formulations have been used to simulate tip-enhanced photoluminescence, surface-enhanced Raman scattering,10 molecular energy transfer,11 and the role of hot-carrier generation in photocatalytic reactions. 12 

1 G. C. Schatz, J. Phys. Chem., 100(31), 12839-12847 (1996) 
2 E. Coccia, F. Troiani, S. Corni, J. Chem. Phys., 148, 204112 (2018) 
3 H. P. Breuer and F. Petruccione, The Theory of Open Quantum Systems, Oxford University Press, (2006) 4 G. Dall’Osto, S. Corni, J. Phys. Chem. A 126, 8088–8100 (2022) 
5 G. Dall’Osto, M. Marsili, S. Corni, E. Coccia, accepted for publication in JCTC 
6 M. Monti, M. Stener, E. Coccia, J. Chem. Phys., 158(8) (2023) 
7 S. Corni, J. Tomasi, J. Chem. Phys., 114(8), 3739-3751 (2001) 
8 S. Pipolo, S. Corni, J. Phys. Chem. C, 120, 50, 28774-28781 (2016)  
9 G. Dall’Osto, G. Gil, S. Pipolo, S. Corni, J. Chem. Phys. 153,18 (2020) 
10 G. Dall’Osto, S. Corni, J. Chem. Phys. 161, 044103 (2024) 
11 C. Coane, et al.,. Comm. Chem., 7(1), 32 (2024)
12 G. Dall'Osto, et al., J. Am. Chem. Soc. 146, 2208−2218 (2024)