Time-dependent simulation of photocurrent-detected two-dimensional spectroscopy of open systems

A new time-domain simulation protocol of two-dimensional electronic spectra with photocurrent detection is presented. Time-dependent density functional theory for open systems at finite temperature is applied to evaluate the photocurrent response to four laser pulses, and a non-perturbative phase-matching approach is implemented to extract the fourth-order photocurrent signal with a desired phase-matching condition. Simulations for an open three-level model indicates that transition dipoles interact resonantly with the incident pulses and that different sample-electrode couplings may be identified by appearance of different peaks/valleys in photocurrent spectra from different electrodes. Moreover, qualitative reproduction of experimental spectra of a PbS quantum dot photocell [Karki et al., Nat. Commun. 5(1), 5869 (2014)] reveals the stimulated electron dynamics.

Automated summary

A new time-domain simulation protocol for two-dimensional electronic spectra with photocurrent detection is presented in this study. Time-dependent density functional theory is applied to evaluate the photocurrent response, and a non-perturbative phase-matching approach is implemented to extract the fourth-order photocurrent signal. The simulations reveal resonant interactions between transition dipoles and incident pulses, and the identification of different sample-electrode couplings based on peaks/valleys in photocurrent spectra. Additionally, the qualitative reproduction of experimental spectra of a PbS quantum dot photocell shows stimulated electron dynamics.