Excitonic Configuration Interaction: Going Beyond the Frenkel Exciton Model

Author(s)

Tomislav Pitesa, Severin Polonius, Leticia González, Sebastian Mai

Abstract

We present the excitonic configuration interaction (ECI) method─a fragment-based analogue of the CI method for electronic structure calculations of multichromophoric systems. It can also be viewed as a generalization of the exciton approach, with the following properties: (i) It constructs the effective Hamiltonian exclusively from monomer calculations. (ii) It employs the strong orthogonality assumption and is exact within McWeeny’s group function theory, thus requiring only one-electron density matrices of the monomer states. (iii) It is agnostic of the monomer electronic structure method, allowing us to use/combine different methods. (iv) It includes an embedding point charge scheme (called excitonic Hartree-Fock, EHF) to improve the accuracy of the monomer states, but such that the effective full-system Hamiltonian is not explicitly dependent on the embedding. (v) It is systematically improvable, by expanding the set of monomer states and by including configurations where two or more monomers are excited (defining the ECIS, ECISD, etc., methods). The performance of ECI is assessed by computing the absorption spectrum of two exemplary multichromophoric systems, using CIS as the monomer electronic structure method. The accuracy of ECI significantly depends on the chosen embedding charges and the ECI expansion. The most accurate assessed combinations─ECIS or ECISD with EHF embedding─yield spectra that agree qualitatively and quantitatively with full-system direct calculations, with deviations of the excitation energies below 0.1 eV. We also show that ECISD based on CIS monomer calculations can predict states where two monomers are excited simultaneously (e.g., triplet-triplet double-local excitations) that are inaccessible in a full-system CIS calculation.

Organisation(s)

Department of Theoretical Chemistry, Research Platform Accelerating Photoreaction Discovery

External organisation(s)

Vienna Doctoral School in Chemistry (DoSChem)

Journal

Journal of Chemical Theory and Computation

Volume

20

Pages

5609-5634

No. of pages

26

ISSN

1549-9618

DOI

https://doi.org/10.1021/acs.jctc.4c00157

Publication date

2024

Peer reviewed

Yes

Austrian Fields of Science 2012

104027 Computational chemistry, 104017 Physical chemistry, 104022 Theoretical chemistry

ASJC Scopus subject areas

Computer Science Applications, Physical and Theoretical Chemistry

Portal url

https://ucrisportal.univie.ac.at/en/publications/excitonic-configuration-interaction-going-beyond-the-frenkel-exciton-model(7a9f66d7-7bfd-4e4e-aaf9-06fd27241a9b).html