An Ab Initio Multiple Cloning Method for Non-Adiabatic Excited-State Molecular Dynamics in NWChem

The recently developed ab initio multiple cloning (AIMC) approach based on the multiconfigurational Ehrenfest (MCE) method provides a powerful and accurate way of describing the excited-state dynamics of molecular systems. The AIMC method is a controlled approximation to nonadiabatic dynamics with a particular strength in the proper description of decoherence effects because of the branching of vibrational wavepackets at a level crossing. Here, we report a new implementation of the AIMC algorithm in the open source NWChem computational chemistry program. The framework combines linear-response time-dependent density functional theory with Ehrenfest mean-field theory to determine the equations of motion for classical trajectories. The multidimensional wave function is decomposed into a superposition of Gaussian coherent states guided by Ehrenfest trajectories (i.e., MCE approach), which can clone with fully quantum mechanical amplitudes and phases. By using an efficient time-derivative based nonadiabatic coupling approach within the AIMC method, all observables are calculated on-the-fly in the nonadiabatic molecular dynamics process. As a representative example, we apply our implementation to study the ultrafast photoinduced electronic and vibrational energy transfer in a pyridine molecule. The effects of the cloning procedure on electronic and vibrational coherence, relaxation and unidirectional energy transfer are discussed. This new AIMC implementation provides a high-level nonadiabatic molecular dynamics framework for simulating photoexcited dynamics in complex molecular systems and experimentally relevant ultrafast spectroscopic probes, such as nonlinear coherent optical and X-ray signals.

Automated summary

The AIMC method, based on the MCE approach, provides an accurate way of describing excited-state dynamics of molecular systems. The algorithm, implemented in NWChem, combines linear-response time-dependent density functional theory with Ehrenfest mean-field theory to determine classical trajectories. By decomposing the multidimensional wave function into Gaussian coherent states guided by Ehrenfest trajectories, the AIMC approach allows for fully quantum mechanical amplitudes and phases in simulations. This new implementation offers a high-level framework for nonadiabatic molecular dynamics simulations in complex molecular systems.