On the importance of multi-configurational and exchange effects in molecular aggregates
Abstract
We present an extension of the Frenkel exciton model to incorporate exchange interactions between monomers in molecular aggregates in conjunction with {a multi-reference electronic structure approach}. Our derivation, {which combines the Frenkel exciton Hamiltonian and the single-electron pair exchange approximation}, yields a non-perturbative, variational expression for the exchange coupling that naturally excludes any basis set superposition error. The method has been implemented in OpenMolcas and enables combination with multi-reference electronic structure techniques. The main objective of the present study is to assess the role of exchange in systems with strong multi-configurational character. Illustrative examples demonstrate how the inclusion of exchange at different levels of approximation can substantially alter the magnitude and sign of intermonomer couplings and thus, for instance, potentially converting the predicted classification of the aggregate from H-type to J-type. Comparison with TDDFT-based couplings highlights significant discrepancies arising from multi-reference effects, double excitations, and Rydberg transitions. Overall, this approach advances the predictive modeling of photophysical and photochemical processes in aggregates of polyacenes, carotenoids, and other systems where multi-configurational and Rydberg states are essential.
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BibTeX
@misc{kaiser2026importance,
title = {{On the importance of multi-configurational and exchange effects in molecular aggregates}},
author = {Andy Kaiser and Francesco Aquilante and Patrick Staschick and Oliver Kühn and Sergey I. Bokarev},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.26393},
eprint = {2609.26393},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.26393},
}
RIS
TY - UNPB
TI - On the importance of multi-configurational and exchange effects in molecular aggregates
AU - Andy Kaiser
AU - Francesco Aquilante
AU - Patrick Staschick
AU - Oliver Kühn
AU - Sergey I. Bokarev
PY - 2026
DA - 2026/09/22
PB - arXiv
DO - 10.48550/arxiv.2609.26393
UR - https://arxiv.org/abs/2609.26393
AB - We present an extension of the Frenkel exciton model to incorporate exchange interactions between monomers in molecular aggregates in conjunction with {a multi-reference electronic structure approach}. Our derivation, {which combines the Frenkel exciton Hamiltonian and the single-electron pair exchange approximation}, yields a non-perturbative, variational expression for the exchange coupling that naturally excludes any basis set superposition error. The method has been implemented in OpenMolcas and enables combination with multi-reference electronic structure techniques. The main objective of the present study is to assess the role of exchange in systems with strong multi-configurational character. Illustrative examples demonstrate how the inclusion of exchange at different levels of approximation can substantially alter the magnitude and sign of intermonomer couplings and thus, for instance, potentially converting the predicted classification of the aggregate from H-type to J-type. Comparison with TDDFT-based couplings highlights significant discrepancies arising from multi-reference effects, double excitations, and Rydberg transitions. Overall, this approach advances the predictive modeling of photophysical and photochemical processes in aggregates of polyacenes, carotenoids, and other systems where multi-configurational and Rydberg states are essential.
ER -