Wavepacket and Reduced-Density Approaches for High-Dimensional Quantum Dynamics: Application to the Nonlinear Spectroscopy of Asymmetrical Light-Harvesting Building Blocks

TL;DR

This paper compares wavepacket and reduced-density matrix methods for simulating high-dimensional quantum dynamics in light-harvesting systems, demonstrating their application to nonlinear spectroscopy and ultrafast excitation-energy transfer in complex molecular models.

Contribution

It introduces a combined approach using ML-MCTDH and HEOM for high-dimensional quantum dynamics and applies it to model ultrafast EET and spectroscopy in asymmetrical PPE dendrimers.

Findings

ML-MCTDH and HEOM methods effectively simulate 93-dimensional vibronic dynamics.

High-frequency vibrational modes are crucial for EET dynamics.

Minimal vibronic-coupling models can predict polarization-sensitive signals.

Abstract

Excitation-energy transfer (EET) and relaxation in an optically excited building block of poly(phenylene ethynylene) (PPE) dendrimers are simulated using wavepackets with the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method and reduced-density matrices with the hierachical equations of motion (HEOM) approach. The dynamics of the ultrafast electronic funneling between the first two excited electronic states in the asymmetrically meta-substituted PPE oligomer with two rings on one branch and three rings on the other side, with a shared ring in between, is treated with 93-dimensional ab initio vibronic-coupling Hamiltonian (VCH) models, either linear or with bilinear and quadratic terms. The linear VCH model is also used to calibrate an open quantum system that falls in a computationally demanding non-perturbative non-Markovian regime. The linear-response absorption and emission spectra are simulated with both the ML-MCTDH and HEOM methods. The latter is further used to explore the nonlinear regime towards two-dimensional (2D) spectroscopy. We illustrate how a minimal VCH model with the two main active bright states and the impulsive-pulse limit in third-order response theory may provide at lower cost polarization-sensitive time-resolved signals that monitor the early EET dynamics. We also confirm the essential role played by the high-frequency acetylenic and quinoidal vibrational modes.