A multiconfigurational wavefunction implementation of the Frenkel exciton model for molecular aggregates

17 April 2023, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


We present an implementation of the Frenkel exciton model into the OpenMolcas program package enabling calculations of collective electronic excited states of molecular aggregates based on a multiconfigurational wavefunction description of the individual monomers. The computational protocol avoids using diabatization schemes and, thus, inherent supermolecule calculations. Additionally, the usage of the Cholesky decomposition of the two-electron integrals entering pair interactions enhances the efficiency of the computational scheme. The application of the method is exemplified for two test systems, that is, a formaldehyde oxime and a bacteriochlorophyll dimer. For the sake of comparison with the dipole approximation, we restrict our considerations to situations where intermonomer exchange can be neglected. The protocol is expected to be beneficial for aggregates composed of molecules with extended $\pi$ systems, unpaired electrons such as radicals or transition metal centers, where it should outperform widely-used methods based on time-dependent density functional theory.


Multiconfiguration wavefunctions
Frenkel exciton
molecular aggregate


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