Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

The Journal of Chemical Physics

Quantum reaction in a condensed phase: Turnover behavior from new adiabatic factorizations and corrections

Steven D. Schwartz

Published Aug 15, 1997• 18 citations
Publisher

Abstract

This paper further investigates quantum activated rate theory from the viewpoint of quantum evolution operators. It is shown that a new adiabatic separation of the quantum system-bath Hamiltonian can, in a single time step, account for quantum turnover behavior at moderate temperatures, and it is also shown how this turnover exponentially vanishes at low temperatures. It is further shown that incorporation of nonadiabatic (interaction representation form) corrections produces quantitatively accurate results at low temperatures, thus extending the applicability of the interaction representation form of nonadiabatic corrections to adiabatic evolution operators.

DOI
10.1063/1.475141

Related papers

The interaction representation and nonadiabatic corrections to adiabatic evolution operators. II. Nonlinear quantum systems

Steven D. Schwartz

This paper reports further applications of the recently developed interaction representation form of infinite order operator corrections to adiabatic evolution operators. Previous work derived the form of the correction, and applied the methodology to a bilinearly coupled system bath model. In this paper we present results on coupled quantum systems in which the coupling is highly nonlinear. The method is both easy to implement and numerically accurate.

The Journal of Chemical Physics•May 22, 1996•8 citations

The interaction representation and nonadiabatic corrections to adiabatic evolution operators

Steven D. Schwartz

This paper presents a new approach to operator resummation corrections to adiabatic evolution operators. It is shown that an infinite order correction produces an operator that is equivalent to a propagator in the interaction representation. For a problem in which the adiabatic approximation assumes that certain degrees of freedom are held fixed, the interaction representation correction is just the interaction propagator of the coupling for these degrees of freedom. This formulation allows simple physical interpretation and simple mathematical evaluation of the full correction. No power series or cumulant methods are needed. Application to double well splitting when coupled to a bath oscillator shows the approach to be highly accurate.

The Journal of Chemical Physics•Jan 22, 1996•16 citations

Adiabatic channel capture theory applied to cold atom–molecule reactions: Li + CaH $\to $ LiH + Ca at 1K

Timur V. Tscherbul, Alexei A Buchachenko

We use quantum and classical adiabatic capture theories to study the chemical reaction Li + CaH LiH + Ca. Using a recently developed ab initio potential energy surface, which provides an accurate representation of long-range interactions in the entrance reaction channel, we calculate the adiabatic channel potentials by diagonalizing the Li-CaH Hamiltonian as a function of the atom-molecule separation. The resulting adiabatic channel potentials are used to calculate both the classical and quantum capture probabilities as a function of collision energy, as well as the temperature dependencies of the partial and total reaction rates. The calculated reaction rate agrees well with the measured value at 1 K (V Singh et al 2012 Phys. Rev. Lett. 108 203201), suggesting that the title reaction proceeds without an activation barrier. The calculated classical adiabatic capture rate agrees well with the quantum result in the multiple-partial-wave regime of relevance to the experiment. Significant differences are found only in the ultracold limit ( mK), demonstrating that adiabatic capture theories can predict the reaction rates with nearly quantitative accuracy in the multiple-partial-wave regime.

arXiv:1412.4575•New Journal of Physics•Mar 20, 2015•16 citations

Quantum adiabatic evolution is not necessary adiabatic: Adiabatic evolution realized by dynamical decoupling

Zhenyu Wang

We decompose the quantum adiabatic evolution as the products of gauge invariant unitary operators and obtain the exact nonadiabatic correction in the adiabatic approximation. A necessary and sufficient condition that leads to adiabatic evolution with geometric phases is provided and we determine that in the adiabatic evolution, while the eigenstates are slowly varying, the eigenenergies and degeneracy of the Hamiltonian can change rapidly. We exemplify this result by the example of the adiabatic evolution driven by parametrized pulse sequences. For driving fields that are rotating slowly with the same average energy and evolution path, fast modulation fields can have smaller nonadiabatic errors than obtained under the traditional approach with a constant amplitude.

•Oct 16, 2012•0 citations

Characterizing Adiabaticity in Quantum Many-Body Systems at Finite Temperature

Amy Skelt, Irene D’Amico

The quantum adiabatic theorem is fundamental to time-dependent quantum systems, but being able to characterize quantitatively an adiabatic evolution in many-body systems can be a challenge. This work demonstrates that the use of appropriate state and particle-density metrics is a viable method to quantitatively determine the degree of adiabaticity in the dynamic of a quantum many-body system. The method applies also to systems at finite temperature, which is important for quantum technologies and quantum thermodynamics related protocols. The importance of accounting for memory effects is discussed via comparison to results obtained by extending the quantum adiabatic criterion to finite temperatures: it is shown that this may produce false readings being quasi-Markovian by construction. As the proposed method makes it possible to characterize the degree of adiabatic evolution by tracking only the system local particle densities, it is potentially applicable to both theoretical calculations of very large many-body systems and to experiments.

•May 19, 2020•4 citations

Asymptotic errors in adiabatic evolution

Thomas D. Cohen, Hyunwoo Oh

The adiabatic theorem in quantum mechanics implies that if a system is in a discrete eigenstate of a Hamiltonian and the Hamiltonian evolves in time arbitrarily slowly, the system will remain in the corresponding eigenstate of the evolved Hamiltonian. Understanding corrections to the adiabatic result that arise when the evolution of the Hamiltonian is slow, but not arbitrarily slow, has become increasingly important, especially since adiabatic evolution has been proposed as a method of state preparation in quantum computing. This paper identifies two regimes, an adiabatic regime in which corrections are generically small and can depend on details of the evolution throughout the path and a hyperadiabatic regime in which the error is given by a form similar to an asymptotic expansion in the inverse of the evolution time with the coefficients depending principally on the behavior at the endpoints. However, the error in this hyperadiabatic regime is neither given by a true asymptotic series nor solely dependent on the endpoints: The coefficients combine the contributions from both endpoints, with relative phase factors that depend on the average spectral gaps along the trajectory, multiplied by the evolution time. The central result of this paper is to identify a quantity, referred to as the typical error, which is obtained by appropriately averaging the error over evolution times that are small compared to the evolution time itself. This typical error is characterized by an asymptotic series and depends solely on the endpoints of the evolution, remaining independent of the details of the intermediate evolution.

arXiv:2501.10641•Physical Review A•Apr 11, 2025•0 citations
This paper further investigates quantum activated rate theory from the viewpoint of quantum evolution operators. It is shown that a new adiabatic separation of the quantum system-bath Hamiltonian can, in a single time step, account for quantum turnover behavior at moderate temperatures, and it is also shown how this turnover exponentially vanishes at low temperatures. It is further shown that incorporation of nonadiabatic (interaction representation form) corrections produces quantitatively accurate results at low temperatures, thus extending the applicability of the interaction representation form of nonadiabatic corrections to adiabatic evolution operators.
This paper presents a new approach to operator resummation corrections to adiabatic evolution operators. It is shown that an infinite order correction produces an operator that is equivalent to a propagator in the interaction representation. For a problem in which the adiabatic approximation assumes that certain degrees of freedom are held fixed, the interaction representation correction is just the interaction propagator of the coupling for these degrees of freedom. This formulation allows simple physical interpretation and simple mathematical evaluation of the full correction. No power series or cumulant methods are needed. Application to double well splitting when coupled to a bath oscillator shows the approach to be highly accurate.
We use quantum and classical adiabatic capture theories to study the chemical reaction Li + CaH LiH + Ca. Using a recently developed ab initio potential energy surface, which provides an accurate representation of long-range interactions in the entrance reaction channel, we calculate the adiabatic channel potentials by diagonalizing the Li-CaH Hamiltonian as a function of the atom-molecule separation. The resulting adiabatic channel potentials are used to calculate both the classical and quantum capture probabilities as a function of collision energy, as well as the temperature dependencies of the partial and total reaction rates. The calculated reaction rate agrees well with the measured value at 1 K (V Singh et al 2012 Phys. Rev. Lett. 108 203201), suggesting that the title reaction proceeds without an activation barrier. The calculated classical adiabatic capture rate agrees well with the quantum result in the multiple-partial-wave regime of relevance to the experiment. Significant differences are found only in the ultracold limit ( mK), demonstrating that adiabatic capture theories can predict the reaction rates with nearly quantitative accuracy in the multiple-partial-wave regime.
We decompose the quantum adiabatic evolution as the products of gauge invariant unitary operators and obtain the exact nonadiabatic correction in the adiabatic approximation. A necessary and sufficient condition that leads to adiabatic evolution with geometric phases is provided and we determine that in the adiabatic evolution, while the eigenstates are slowly varying, the eigenenergies and degeneracy of the Hamiltonian can change rapidly. We exemplify this result by the example of the adiabatic evolution driven by parametrized pulse sequences. For driving fields that are rotating slowly with the same average energy and evolution path, fast modulation fields can have smaller nonadiabatic errors than obtained under the traditional approach with a constant amplitude.
The quantum adiabatic theorem is fundamental to time-dependent quantum systems, but being able to characterize quantitatively an adiabatic evolution in many-body systems can be a challenge. This work demonstrates that the use of appropriate state and particle-density metrics is a viable method to quantitatively determine the degree of adiabaticity in the dynamic of a quantum many-body system. The method applies also to systems at finite temperature, which is important for quantum technologies and quantum thermodynamics related protocols. The importance of accounting for memory effects is discussed via comparison to results obtained by extending the quantum adiabatic criterion to finite temperatures: it is shown that this may produce false readings being quasi-Markovian by construction. As the proposed method makes it possible to characterize the degree of adiabatic evolution by tracking only the system local particle densities, it is potentially applicable to both theoretical calculations of very large many-body systems and to experiments.
The adiabatic theorem in quantum mechanics implies that if a system is in a discrete eigenstate of a Hamiltonian and the Hamiltonian evolves in time arbitrarily slowly, the system will remain in the corresponding eigenstate of the evolved Hamiltonian. Understanding corrections to the adiabatic result that arise when the evolution of the Hamiltonian is slow, but not arbitrarily slow, has become increasingly important, especially since adiabatic evolution has been proposed as a method of state preparation in quantum computing. This paper identifies two regimes, an adiabatic regime in which corrections are generically small and can depend on details of the evolution throughout the path and a hyperadiabatic regime in which the error is given by a form similar to an asymptotic expansion in the inverse of the evolution time with the coefficients depending principally on the behavior at the endpoints. However, the error in this hyperadiabatic regime is neither given by a true asymptotic series nor solely dependent on the endpoints: The coefficients combine the contributions from both endpoints, with relative phase factors that depend on the average spectral gaps along the trajectory, multiplied by the evolution time. The central result of this paper is to identify a quantity, referred to as the typical error, which is obtained by appropriately averaging the error over evolution times that are small compared to the evolution time itself. This typical error is characterized by an asymptotic series and depends solely on the endpoints of the evolution, remaining independent of the details of the intermediate evolution.