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The Moving Born-Oppenheimer Approximation

Published 24 Feb 2025 in quant-ph, cond-mat.quant-gas, cond-mat.stat-mech, and physics.chem-ph | (2502.17557v2)

Abstract: We develop a mixed quantum-classical framework, dubbed the Moving Born-Oppenheimer Approximation (MBOA), to describe the dynamics of slow degrees of freedom (DOFs) coupled to fast ones. As in the Born-Oppenheimer Approximation (BOA), the fast degrees of freedom adiabatically follow a state that depends on the slow ones. Unlike the BOA, this state depends on both the positions and the momenta of the slow DOFs. We study several model systems: a spin-1/2 particle and a spinful molecule moving in a spatially inhomogeneous magnetic field, and a gas of fast particles coupled to a piston. The MBOA reveals rich dynamics for the slow degree of freedom, including reflection, dynamical trapping, and mass renormalization. It also significantly modifies the state of the fast DOFs. For example, the spins in the molecule are entangled and squeezed, while the gas of fast particles develops gradients that are synchronized with the motion of the piston for a long time. The MBOA can be used to describe both classical and quantum systems and has potential applications in molecular dynamics, state preparation, and quantum sensing.

Summary

The Moving Born-Oppenheimer Approximation

The paper "The Moving Born-Oppenheimer Approximation" introduces a refined approach to study the dynamics of systems featuring both slow and fast degrees of freedom (DOFs). Conventionally, the Born-Oppenheimer Approximation (BOA) predicates that fast DOFs adiabatically follow the instantaneous ground state determined by the configurations of slow DOFs, fundamentally reducing problem dimensionality. This traditional framework is pivotal but falls short in contexts characterized by rapid motion of slow DOFs or negligible energy gaps between fast DOF levels.

The authors propose a novel extension coined the Moving Born-Oppenheimer Approximation (MBOA), modifying the adiabatic conditions inherent in the BOA by incorporating the dynamics of both the position and momentum of the slow DOFs. This nuanced approach provides enhanced accuracy in predicting the equilibrium states that fast DOFs adiabatically follow during system evolution, crucially including effects from pseudo-forces akin to those found in the classical mechanics of rotating or accelerated frames—the Coriolis and centrifugal forces.

In the MBOA framework, the evolution of the fast DOFs is described by a moving frame Hamiltonian. This Hamiltonian encompasses not only the standard potential energy surfaces but also momentum-dependent terms proportional to an adiabatic gauge potential (AGP), which arises from the geometric nature of quantum mechanics. The AGP effectively shifts the canonical momentum, thus influencing both equilibrium and dynamical properties and potentially entangling the fast DOFs. The method is particularly adept at capturing quantum coherence and non-adiabatic transitions interlaced with classical dynamics.

Several model systems are analyzed to demonstrate the potency of the MBOA: a spin-1/2 particle and spinful molecule in non-uniform magnetic fields, and a classical gas-quasi-piston system. Notably, the MBOA framework accurately predicts reflection and trapping dynamics for slow DOFs and generates spin entanglement and squeezing among fast DOFs—phenomena overlooked by the BOA. The scheme also adeptly manages classical systems by deriving effective Hamiltonians that account for mass-renormalization and synchronization effects, enabled by trajectory-preserving transformations.

The MBOA's capability to derive non-trivial dynamics and rich equilibrium states portends significant implications and applications spanning quantum sensing and molecular dynamics to more theoretical pursuits like adiabatic quantum computation and time-dependent density functional theory that integrate beyond-standard adiabatic corrections.

Speculatively, future developments will likely address incorporating incoherent transitions between dressed states, propelling the MBOA towards a more nuanced understanding of systems where energy level densities play pivotal roles. This endeavor opens doors to constructing refined computational schemes that could transform our approach to addressing non-adiabatic effects, especially in chemistries and ultrafast processes where conventional approaches become infeasible.

In conclusion, the MBOA lays a groundwork not just for specifying more intricate and accurate models but also for traversing the conceptual boundaries between quantum and classical dynamics, potentially palliating computational and theoretic challenges across disciplines. This development marks a notable trajectory in understanding complex system dynamics under nuanced adiabatic conditions, further enhancing the field's capacity to simulate, predict, and harness molecular and quantum behaviors.

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