Spectral line shapes in the condensed phase contain information about various dynamical processes that modulate the transition energy, such as microscopic dynamics, inter- and intramolecular couplings. In this talk I will explore and describe the role of different physical phenomena that arise from the peculiarities of dissipative dynamics in multidimensional spectra. The methodology will be...
Ultrafast processes in condensed phase photoexcited molecular systems involve the transition from a coherent dynamical regime – where a precise phase relation exists between different wave packet components – to incoherent "classical-like" dynamics. The decoherence process is driven the dissipation due to the surrounding molecular environment.
From the computational viewpoint, modelling...
We have developed a fully quantum, numerically accurate wave function-based approach for the calculation of third-order spectroscopic signals of polyatomic molecules and molecular aggregates at finite temperature including statiuc disorder effects. The systems are described by multimode nonadiabatic vibronic-coupling Hamiltonians, in which diagonal terms are treated in harmonic approximation,...
It is well accepted that the most general case of photoinduced reaction dynamics occurs through non-adiabatic transitions. The complex panorama of potential energy surfaces describing the excited states of polyatomic molecules is characterized by non-adiabatic crossings and the presence of multiple conical intersections. A conical intersection (CI) is a 3N-8-dimension hypersurface of...
Fewest-switches surface hopping (FSSH) is one of the most popular methods for simulating photochemical experiments [1], even though it suffers from problems of inconsistency and overcoherence that significantly degrade the accuracy of its results. In particular, FSSH is unable to correctly describe the dynamics under strong electromagnetic pulses [2,3], such that a fully satisfactory approach...
