A TDDFT/MMPol/PCM model for the simulation of exciton-coupled circular dichroism spectra
文献信息
Sandro Jurinovich, Gennaro Pescitelli, Lorenzo Di Bari, Benedetta Mennucci
We present a quantum-mechanical excitonic model to compute CD spectra of multichromophoric compounds. All the quantities needed to build the excitonic Hamiltonian are obtained through QM calculations in which the interactions among the chromophoric units are described in terms of full transition densities instead of reverting to the common dipole–dipole approximation. Environmental effects due to solvation and the perturbation due to other surrounding units are included in a self-consistent way using a polarizable continuum model and a polarizable MM approach, respectively. The application to two different coordination compounds shows that the method not only successfully reproduces the experimental spectra but it can also be used to investigate and dissect the role of the various effects contributing to the final result, such as intra-molecular coupling terms and environment effects. This method can therefore represent an ab initio-alternative to the widely applied matrix-based approach, and in principle it has the advantage of not requiring the knowledge of any experimental data a priori or the transition dipole parameters.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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