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Updated: Apr 19, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
In search of a rational dressing of intermediate effective Hamiltonians
Barthélémy Pradines1,2, Nicolas Suaud1,2, Jean-Paul Malrieu1,2
1Laboratoire de Chimie et Physique Quantiques, IRSAMC, Université de Toulouse 3 Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex, France.
Abstract:
The intermediate effective Hamiltonians are designed to provide M exact energies and the components of the corresponding eigenvectors in the N-dimensional model space, with N > M. The effective Hamiltonian is not entirely defined by these N × M conditions, and several dressings of the Hamiltonian matrix in the model space are possible. Some of them lead to unreliable N - M roots associated with the intermediate model space. This defect appears dramatically when one refers to the weak separability property, namely, the fact that in a noninteracting A···B problem where the model space only involves excitations on A, the consideration of the excitations on B should not affect the spectrum of A. We suggest variants that should maintain the physical meaning of the intermediate roots. Numerical comparisons illustrate the relevance of this proposal.
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