Quasi-Diabatic Scheme for Non-adiabatic On-the-fly Simulations

TL;DR

This paper introduces the first ab-initio on-the-fly implementation of the Quasi-Diabatic scheme, facilitating non-adiabatic simulations by bridging diabatic dynamics and adiabatic electronic structure calculations, thus expanding the toolkit for complex molecular dynamics.

Contribution

It presents a novel application of the Quasi-Diabatic scheme for ab-initio on-the-fly non-adiabatic simulations, enabling seamless integration with existing electronic structure methods.

Findings

Enables use of various diabatic quantum dynamics approaches

Allows realistic test cases like ethylene photodynamics

Avoids reformulating equations of motion or constructing global diabatic surfaces

Abstract

This paper provides the first ab-initio on-the-fly example of using the Quasi-Diabatic (QD) scheme for non-adiabatic simulations with diabatic dynamics approaches. The QD scheme provides a seamless interface between diabatic quantum dynamics approaches and {\it adiabatic} electronic structure calculations. It completely avoids additional theoretical efforts to reformulate the equation of motion from diabatic to adiabatic representation, or construct global diabatic surfaces. This scheme enables many recently developed diabatic quantum dynamics approaches for ab-inito on-the-fly simulations, providing the non-adiabatic community a wide variety of approaches (such as the real-time path integral method and symmetric quasi-classical approach) beyond the well-explored methods (like trajectory surface-hopping or ab-initio multiple-spawning). The QD scheme also enables using realistic test cases (like ethylene photodynamics) that go beyond simple model systems to assess the accuracy and limitation of recently developed quantum dynamics approaches.