Efficient and reliable modeling of large $\pi$-electron systems with the Pariser--Parr--Pople Hamiltonian and pCCD-based methods

TL;DR

This paper presents a combined approach using the Pariser--Parr--Pople Hamiltonian and pCCD-based methods to efficiently model the electronic structure of large $ au$-conjugated systems, demonstrating reliability and scalability.

Contribution

It introduces a novel integration of the PPP model with pCCD methods, including a new parameterization for better accuracy in large $ au$-electron systems.

Findings

pCCD-based methods reliably predict electronic properties of PAHs.

The generalized Coulomb interaction parameterization improves model accuracy.

The approach is scalable for large $ au$-conjugated systems.

Abstract

Model Hamiltonians offer a cost-effective way to capture the key physics of large $\pi$-conjugated systems. In this work, we combine the Pariser--Parr--Pople (PPP) model Hamiltonian with pair Coupled Cluster Doubles (pCCD)-based methods to study the ground- and excited-state electronic structures of polycyclic aromatic hydrocarbons (PAHs). The model Hamiltonian implementation is done in the open-source PyBEST software package, where numerous pCCD-type models are available. We investigate canonical Hartree--Fock and natural pCCD-optimized orbitals to compute ground- and excited-state properties using pCCD and its linear response extension. Their performance is compared with configuration-interaction-based methods. Finally, we introduce a generalized parameterization of the long-range Coulomb interaction using a rescaled interaction prefactor to adopt the PPP parameters to the pCCD approach and the localized nature of the pCCD orbitals. Our results demonstrate that pCCD-based methods, combined with a suitably parametrized PPP model, provide a reliable and scalable framework for studying the optoelectronic properties of large $\pi$-extended systems relevant to organic electronics.