Theory of two-photon absorption in poly(diphenyl) polyacetylenes

TL;DR

This paper provides a theoretical analysis of two-photon absorption in the conjugated polymer PDPA, revealing anisotropic nonlinear optical properties and energy-dependent polarization characteristics through advanced quantum chemical models.

Contribution

It introduces a comprehensive theoretical framework combining independent-particle and correlated-electron models to study nonlinear optical responses in PDPA, highlighting anisotropy and energy scale distinctions.

Findings

Polymer exhibits highly anisotropic nonlinear optical response.

Low-energy response polarized along conjugation direction.

High-energy response polarized perpendicular to conjugation.

Abstract

In this paper, we present a theoretical study of the nonlinear optical response of the newly discovered conjugated polymer poly(diphenyl)polyacetylene (PDPA). In particular, we compute the third-order nonlinear susceptibility corresponding to two-photon absorption process in PDPA using: (a) independent-particle H\"uckel model, and (b) using the correlated-electron Pariser-Parr-Pople (P-P-P) model coupled with various configuration-interaction methodologies such as the singles-configuration-interaction (SCI), the multi-reference-singles-doubles CI (MRSDCI), and the quadruples-CI (QCI) method. At all levels of theory, the polymer is found to exhibit highly anisotropic nonlinear optical response, distributed over two distinct energy scales. The low-energy response is predominantly polarized in the conjugation direction, and can be explained in terms of chain-based orbitals. The high-energy response of the polymer is found to be polarized perpendicular to the conjugation direction, and can be explained in terms of orbitals based on the side phenylene rings. Moreover, the intensity of the nonlinear optical response is also enhanced as compared to the corresponding polyenes, and can be understood in terms of reduced optical gap.