A general purpose Fortran 90 electronic structure program for conjugated systems using Pariser-Parr-Pople model

TL;DR

This paper introduces a versatile Fortran 90 program for electronic structure calculations of conjugated systems using the Pariser-Parr-Pople model, capable of solving Hartree-Fock, correlation, optical spectra, and band structures.

Contribution

The program uniquely integrates multiple computational methods and properties calculations for conjugated systems within a single code, enhancing research capabilities.

Findings

Successfully computes electronic properties of various conjugated systems.

Capable of calculating optical absorption spectra at multiple levels.

Allows external electric field calculations for polarizabilities.

Abstract

Pariser-Parr-Pople (P-P-P) model Hamiltonian has been used extensively over the years to perform calculations of electronic structure and optical properties of $\pi$-conjugated systems successfully. In spite of tremendous successes of \emph{ab initio} theory of electronic structure of large systems, the P-P-P model continues to be a popular one because of a recent resurgence in interest in the physics of $\pi$-conjugated polymers, fullerenes and other carbon based materials. In this paper, we describe a Fortran 90 computer program developed by us, which uses P-P-P model Hamiltonian to not only solve Hartree-Fock (HF) equation for closed- and open-shell systems, but also for performing correlation calculations at the level of single configuration interactions (SCI) for molecular systems. Moreover, the code is capable of computing linear optical absorption spectrum at various levels, such as, tight binding (TB) Hueckel model, HF, SCI, and also of calculating the band structure using the Hueckel model. The code also allows the user to solve the HF equation in the presence of finite external electric field, thus, permitting calculations of quantities such as static polarizabilities and electro-absorption spectra. We demonstrate the capabilities of our code by performing calculations of various properties on conjugated systems such as $trans$-polyacetylene ($t$-PA), poly-\emph{para}-phenylene (PPP), poly-\emph{para}-phenylene-vinylene (PPV), \textit{oligo}-acenes, and graphene nanodisks.