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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

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Published on: May 27, 2020

Multiconfigurational short-range on-top pair-density functional theory.

Frederik Kamper Jørgensen¹, Erik Rosendahl Kjellgren¹, Hans Jørgen Aagaard Jensen¹

¹Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, DK-5230 Odense M, Denmark.

The Journal of Chemical Physics

|January 15, 2025

Summary

This summary is machine-generated.

We introduce a new computational model, multiconfigurational self-consistent on-top pair-density functional theory (MC-srPDFT), that accurately describes strongly correlated systems. This advanced method overcomes limitations of previous density functional theory approaches, improving calculations for molecular systems.

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Area of Science:

Quantum Chemistry
Computational Chemistry
Materials Science

Background:

Existing density functional theory (DFT) methods, including multiconfigurational short-range DFT (MC-srDFT), face challenges like self-interaction errors and incorrect energy degeneracies for certain molecular states.
These deficiencies limit the accurate description of strongly correlated electronic systems and excited states.

Purpose of the Study:

To present the theory and implementation of a novel, fully variational hybrid model: multiconfigurational self-consistent on-top pair-density functional theory (MC-srPDFT).
To address and correct the limitations of previous MC-srDFT models, particularly concerning self-interaction errors and state degeneracies.

Main Methods:

Developed a fully variational hybrid model using on-top pair density as an auxiliary variable, replacing spin density.
Employed a long-range version of the on-top pair density and a second-order optimization algorithm for robust convergence.
Applied the MC-srPDFT model to calculate ground and excited states for various molecules, including H2, N2, Cr2, and ethene.

Main Results:

The MC-srPDFT model successfully corrects self-interaction errors and ensures correct degeneracy between different spin states at dissociation.
Calculations for H2, N2, Cr2, and ethene demonstrate the model's accuracy for ground and excited states, including dissociation curves and rotational barriers.
Results showed invariance to the choice of the MS value for triplet curves, indicating model robustness.

Conclusions:

MC-srPDFT offers a significant advancement in computational chemistry, providing accurate descriptions for challenging strongly correlated systems.
The model's ability to overcome DFT limitations opens new possibilities for studying complex molecular properties and reactions.
This work establishes MC-srPDFT as a reliable tool for both ground and excited-state calculations in quantum chemistry.