Time-dependent Density Matrix Renormalization Group Quantum Dynamics for Realistic Chemical Systems

TL;DR

This paper benchmarks four tDMRG quantum dynamics methods against MCTDH and experiments, demonstrating that 2TDVP effectively models complex chemical systems with strong electron-vibration interactions.

Contribution

It provides a comprehensive comparison of four tDMRG methods for realistic chemical systems, highlighting the accuracy and efficiency of 2TDVP in complex quantum dynamics simulations.

Findings

2TDVP method accurately models large chemical systems.

tDMRG methods outperform MCTDH in efficiency.

Optimal parameters balance accuracy and computational cost.

Abstract

Electronic and/or vibronic coherence has been found by recent ultrafast spectroscopy experiments in many chemical, biological and material systems. This indicates that there are strong and complicated interactions between electronic states and vibration modes in realistic chemical systems. Therefore, simulations of quantum dynamics with a large number of electronic and vibrational degrees of freedom are highly desirable. Due to the efficient compression and localized representation of quantum states in the matrix-product state (MPS) formulation, time-evolution methods based on the MPS framework, which we summarily refer to as tDMRG (time-dependent density-matrix renormalization group) methods, are considered to be promising candidates to study the quantum dynamics of realistic chemical systems. In this work, we benchmark the performances of four different tDMRG methods, including global Taylor, global Krylov, local one-site and two-site time-dependent variational principle (1TDVP and 2TDVP), with a comparison to multi-configuration time-dependent Hartree (MCTDH) and experimental results. Two typical chemical systems of internal conversion and singlet fission are investigated, one containing strong and high-order local and non-local electron-vibration couplings, the other exhibiting a continuous phonon bath. The comparison shows that the tDMRG methods (particularly, the 2TDVP method) can describe the full quantum dynamics in large chemical systems accurately and efficiently. Several key parameters in the tDMRG calculation including the truncation error threshold, time interval and ordering of local sites were also investigated to strike the balance between efficiency and accuracy of results.