DMRG Calculations of the Low-lying Excitations and Nonlinear Optical Properties of poly(para-phenylene)

TL;DR

This paper uses DMRG and a 2-MO model to accurately calculate low-lying excitations and nonlinear optical properties of poly(para-phenylene), aligning well with experimental data and revealing tightly bound excitons and key electronic states.

Contribution

It introduces a combined DMRG and 2-MO modeling approach to predict excitations and nonlinear optical responses in PPP, validated against experimental spectra.

Findings

Existence of a band of Bu excitons below band states

Lowest exciton is 3.3 eV above ground, matching experiments

Main EA features are explained by five key states

Abstract

The two state molecular orbital (2-MO) model of the phenyl based semiconductors is used to calculate the low-lying spectra of the Ag and Bu states of poly(para-phenylene) (PPP). The model parameters are determined by fitting its predictions to exact Pariser-Parr-Pople model calculations of benzene and biphenyl, and it is solved using the density matrix renormalisation group method. It is shown that there exists a band of Bu (s-wave) excitons below the band states. In the long chain limit the lowest exciton is situated 3.3 eV above the ground state, consistent with experimental data. The calculated particle-hole separation of these excitons indicates that they are tightly bound, extending over only a few repeat units. The lowest band state is found to be a covalent 2Ag state, whose energy almost coincides with the charge gap Eg. Lying just above the 2Ag state is a band Bu state (the nBu state). The particle-hole separation of the band states scales linearly with oligomer size. The binding energy of the 1Bu exciton is determined rigorously as 0.74 eV. The dipole matrix elements and oscillator strengths for the transitions between the lowest Ag and Bu states are calculated and the NLO properties of PPP, such as electroabsorption (EA) and third harmonic generation, are investigated. A comparison of the EA spectrum with the experimental data shows that the main features of the experimental spectrum are well described by the 2-MO Hamiltonian. Only five states account for most of the calculated EA. These are the 1Ag, 1Bu, 2Ag, nBu and another band Ag state, the kAg, thus confirming the essential states model. An analysis of the particle excitation weight of these states indicates that they are predominately single particle in character.