Open-system Renner–Teller dynamics with quantum Brownian motion within a Markovian Caldeira–Leggett limit

An open-system, coordinate-resolved formulation of Renner-Teller (RT) rovibronic dynamics is developed by embedding a two-state RT Hamiltonian in a quantum Brownian motion environment within the high-temperature, Markovian Caldeira-Leggett (CL) master-equation limit. I derive channel-resolved local balance laws for RT wavepacket densities in Jacobi coordinates, in which the Hermitian kinetic operator yields a curvilinear probability-current divergence, the RT off-diagonal blocks generate antisymmetric interchannel source-sink exchange, and the CL dissipator supplies coordinate-wise friction and momentum-diffusion corrections. These contributions are evaluated on a parity-adapted ΩK,M,ΛJ,p basis and used to construct a grid-resolved dominance analysis of the intersurface transfer-layer density for near-linear N2O. Application to the near-linear RT manifold of N2O illustrates how electronically controlled RT driving (through the adiabatic splitting ΔV and mixing angle α12) and bath-mediated dissipation jointly regulate the emergence, transport, reactivation, and late-time spreading of an intersurface transfer-layer density, providing a grid-resolved diagnostic that directly links wavepacket motion to environment-induced relaxation and decoherence.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2026-04-16
DOI
https://doi.org/10.1063/5.0325114
Primary Topic
Spectroscopy and Quantum Chemical Studies
Type
article
Field-Weighted Citation Impact
0.00

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article

Open-system Renner–Teller dynamics with quantum Brownian motion within a Markovian Caldeira–Leggett limit

Mohammad Noh Daud
The Journal of Chemical Physics
Spectroscopy and Quantum Chemical Studies
article

Open-system Renner–Teller dynamics with quantum Brownian motion within a Markovian Caldeira–Leggett limit

Mohammad Noh Daud
article en

Abstract

An open-system, coordinate-resolved formulation of Renner-Teller (RT) rovibronic dynamics is developed by embedding a two-state RT Hamiltonian in a quantum Brownian motion environment within the high-temperature, Markovian Caldeira-Leggett (CL) master-equation limit. I derive channel-resolved local balance laws for RT wavepacket densities in Jacobi coordinates, in which the Hermitian kinetic operator yields a curvilinear probability-current divergence, the RT off-diagonal blocks generate antisymmetric interchannel source-sink exchange, and the CL dissipator supplies coordinate-wise friction and momentum-diffusion corrections. These contributions are evaluated on a parity-adapted ΩK,M,ΛJ,p basis and used to construct a grid-resolved dominance analysis of the intersurface transfer-layer density for near-linear N2O. Application to the near-linear RT manifold of N2O illustrates how electronically controlled RT driving (through the adiabatic splitting ΔV and mixing angle α12) and bath-mediated dissipation jointly regulate the emergence, transport, reactivation, and late-time spreading of an intersurface transfer-layer density, providing a grid-resolved diagnostic that directly links wavepacket motion to environment-induced relaxation and decoherence.

The Journal of Chemical PhysicsVol. 164(15)
University of Malaya (MY)
Universiti Malaya
Openalex Percentile: Top 10%
Spectroscopy and Quantum Chemical Studies
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