Tensor Network HEOM study of cavity induced modifications of reaction rates in vibrational strong coupling.
ORAL
Abstract
Recent experiments have indicated that strong coupling between cavity photon modes and molecular vibrations might be able to alter chemical reaction rates and yields.
Understanding the underlying mechanisms that produce these effects is key in harnessing such observations for technological advancement. Yet, experimental and theoretical challenges remain unsolved and a full solution to this problem remains elusive despite the efforts of several research groups to demystify chemistry under vibrational strong coupling.
We will adress some of these challenges by considering a reaction coordinate embedded in a gaussian environment. This gaussian environment consists of the cavity mode(s), solvent degrees of freedom and any additional harmonic vibrational spectator modes. The dynamics for the resulting open quantum system can be solved for, using the hierarchical equation of motion (HEOM) approach, where the continuum of bath modes is accurately approximated by a handful of unphysical modes that are then time-evolved with the system, using tensor network based algorithms such as tdvp.
Our approach is flexible, as it accounts for nearly arbitrary gaussian environments and multiple reaction coordinates, which allows us to study the interplay of competing pathways, realistic cavities and notions of collective behaviour.
Understanding the underlying mechanisms that produce these effects is key in harnessing such observations for technological advancement. Yet, experimental and theoretical challenges remain unsolved and a full solution to this problem remains elusive despite the efforts of several research groups to demystify chemistry under vibrational strong coupling.
We will adress some of these challenges by considering a reaction coordinate embedded in a gaussian environment. This gaussian environment consists of the cavity mode(s), solvent degrees of freedom and any additional harmonic vibrational spectator modes. The dynamics for the resulting open quantum system can be solved for, using the hierarchical equation of motion (HEOM) approach, where the continuum of bath modes is accurately approximated by a handful of unphysical modes that are then time-evolved with the system, using tensor network based algorithms such as tdvp.
Our approach is flexible, as it accounts for nearly arbitrary gaussian environments and multiple reaction coordinates, which allows us to study the interplay of competing pathways, realistic cavities and notions of collective behaviour.
*All calculations were performed using the computational facilities of the Flatiron Institute. The Flatiron Institute is a division of the Simons Foundation.
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Presenters
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Jonas Vinther
- Center for Computational Quantum Physics, Flatiron Institute