In recent years, conjugated polymers are attracting considerable interest in view of their lightdependent torsional reorganization around the p-conjugated backbone, which determines peculiar light-emitting properties. Motivated by the interest in designing conjugated polymers with tunable photoisomerization pathways, we devised a computational framework to enhance the sampling of the polymer conformational space and at the same time estimate ground to excited-state free-energy differences. This scheme is based on a combination of Hamiltonian Replica Exchange (REM), Parallel Bias metadynamics, and free-energy perturbation theory. In our scheme, each REM replica samples different intermediate states connecting the ground to the first two excited states, which are characterized by TD-DFT simulations at the B3LYP/6-31G* level of theory. We applied the method on a 5-mer of poly(9,9-dioctylfluoren-2,7-diyl) and compared the results with the emission energies measured experimentally, showing a quantitative agreement with the prediction provided by our simulation framework.
The comprehensive characterization of Intramolecular Charge Transfer (ICT) stemming in push-pull molecules with a delocalized π-system of electrons is noteworthy for a bespoke design of organic materials, spanning widespread applications from photovoltaics to nanomedicine imaging devices. Photo-induced ICT is characterized by structural reorganizations, which allows the molecule to adapt to the new electronic density distribution. Herein, we discuss recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles. We focus the discussion on femtosecond Transient Absorption Spectroscopy (TAS) enabling us to follow the transition from a Locally Excited (LE) state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms. In many cases, the charge transfer transition is accompanied by structural rearrangements, such as the twisting or molecule planarization. The possibility of an accurate prediction of the charge-transfer occurring in complex molecules and molecular materials represents an enormous advantage in guiding new molecular and materials design. We briefly report on recent advances in ultrafast multidimensional spectroscopy, in particular, Two-Dimensional Electronic Spectroscopy (2DES), in unraveling the ICT nature of push-pull molecular systems. A theoretical description at the atomistic level of photo-induced molecular transitions can predict with reasonable accuracy the properties of photoactive molecules. In this framework, the review includes a discussion on the advances from simulation and modeling, which have provided, over the years, significant information on photoexcitation, emission, charge-transport, and decay pathways. Density Functional Theory (DFT) coupled with the Time-Dependent (TD) framework can describe electronic properties and dynamics for a limited system size. More recently, Machine Learning (ML) or deep learning approaches, as well as free-energy simulations containing excited state potentials, can speed up the calculations with transferable accuracy to more complex molecules with extended system size. A perspective on combining ultrafast spectroscopy with molecular simulations is foreseen for optimizing the design of photoactive compounds with tunable properties.
The π-rich rings of conjugated polymers and molecular rotors shape their typical properties, allowing a variety of chemical and photoresponsive phenomena. Herein, we present a computational method in the framework of classical simulations to estimate the free-energy gap between ground and excited states of oligofluorenes, a class of molecular rotors widely used in optoelectronic devices due to the inner torsional rotation triggered by light irradiation. We devised multiple sets of free-energy simulations in combination with free-energy perturbation theory to predict the freeenergy gap between the ground and the first excited state. The computed excitation energies show good agreement with experiments. The approach herein presented allows to achieve at the same time comprehensive sampling of the conformational landscape and accurate estimates of the excited state free-energy landscapes.
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