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Related Experiment Video

Updated: Jan 22, 2026

Author Spotlight: Evaluation of Protein-Condensate Dynamics in Live Human Cells
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Simulating conical intersection dynamics in the condensed phase with hybrid quantum master equations.

Addison J Schile1, David T Limmer1

  • 1Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.

The Journal of Chemical Physics
|July 6, 2019
PubMed
Summary
This summary is machine-generated.

This study introduces a new computational framework for simulating quantum system dynamics near conical intersections. The method accurately models complex molecular processes, revealing how energy scales influence relaxation and quantum yields.

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Area of Science:

  • Quantum dynamics
  • Theoretical chemistry
  • Spectroscopy

Background:

  • Conical intersections are crucial for ultrafast processes in molecules.
  • Simulating these dynamics in open quantum systems is computationally challenging.
  • Disparate timescales in nuclear and electronic motion complicate modeling.

Purpose of the Study:

  • To develop a versatile computational framework for simulating relaxation dynamics through conical intersections in open quantum systems.
  • To accurately model systems with multiple degrees of freedom exhibiting varying time and energy scales.
  • To investigate the influence of system-bath interactions on quantum yields.

Main Methods:

  • A hybrid approach combining exact wavepacket dynamics for strongly coupled modes with approximations for weakly coupled modes.
  • Utilizing the time-convolutionless master equation for fast degrees of freedom.
  • Employing the frozen-mode extension to second-order quantum master equations for slow degrees of freedom.
  • Benchmarking against numerically exact results for pyrazine internal conversion and rhodopsin photoisomerization.

Main Results:

  • The framework accurately reproduces results for benchmark systems.
  • Quantum yield dependence on reorganization energy varies significantly between Markovian and non-Markovian baths.
  • Demonstrated the interplay between dissipation and decoherence in condensed-phase conical intersection dynamics.

Conclusions:

  • The developed framework provides an efficient and accurate method for studying complex quantum dynamics.
  • Understanding bath characteristics (Markovian vs. non-Markovian) is critical for predicting quantum yields.
  • Highlights the importance of considering system-bath interactions in photochemical processes.