Pariser-Parr-Pople Model based Configuration-Interaction Study of Linear Optical Absorption in Lower-Symmetry Polycyclic Aromatic Hydrocarbon Molecules

TL;DR

This study uses the Pariser-Parr-Pople model with configuration interaction to analyze the optical absorption of lower-symmetry polycyclic aromatic hydrocarbons, revealing size-dependent spectral shifts and validating results against experimental data.

Contribution

It introduces a detailed electron-correlated computational approach for lower-symmetry PAHs, incorporating long-range Coulomb interactions for accurate optical property predictions.

Findings

Optical spectra shift to lower energies with increasing molecule size.

First optical peak has moderate intensity, higher peaks are more intense.

Computed spectra agree well with experimental data.

Abstract

The electronic and optical properties of various polycyclic aromatic hydrocarbons (PAHs) with lower symmetry, namely, benzo[ghi]perylene (C$_{22}$H$_{12}$), benzo[a]coronene (C$_{28}$H$_{14}$), naphtho[2,3a]coronene (C$_{32}$H$_{16}$), anthra[2,3a]coronene (C$_{36}$H$_{18}$), and naphtho[8,1,2-abc]coronene (C$_{30}$H$_{14}$) were investigated. For the purpose, we performed electron-correlated calculations using screened, and standard parameters in the $\pi$-electron Pariser-Parr-Pople (PPP) Hamiltonian, and the correlation effects were included, both for ground and excited states, using the multi-reference singles-doubles configuration-interaction (MRSDCI) methodology. PPP model Hamiltonian includes long-range Coulomb interactions, which increase the accuracy of our calculations. The results of our calculations predict that, with the increasing sizes of the coronene derivatives, optical spectra are red shifted, and the optical gaps decrease. In each spectrum, the first peak representing the optical gap is of moderate intensity, while the more intense peaks appear at higher energies. Our computed spectra are in good agreement with the available experimental data. For the purpose of comparison, we also performed first-principles time-dependent density-functional theory (TDDFT) calculations of the optical gaps of these molecules using Gaussian basis functions, and found that they yielded values lower than our CI results.