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arXiv:2201.12388 · New Journal of Physics

Nonadiabatic decay of metastable states on coupled linear potentials

Alisher Duspayev, Ansh Shah, Georg A. Raithel

Published May 1, 2022• 3 citations
arXivHTMLPDF

Abstract

Abstract Avoided crossings of level pairs with opposite slopes can form potential-energy minima for the external degree of freedom of quantum particles, giving rise to metastable states on the avoided crossings (MSACs). Nonadiabatic decay of MSACs is studied by solving the two-component Schrödinger equation in diabatic and adiabatic representations. Non-perturbative lifetime values are found by evaluating wave function flux and scattering phases of time-independent solutions, as well as wave-function decay of time-dependent solutions. The values from these methods generally agree well, validating the utilized approaches. As the adiabaticity parameter, V, of the system is increased by about a factor of ten across the mixed diabatic/adiabatic regime, the MSAC character transitions from marginally to highly stable, with the lifetimes increasing by about ten orders of magnitude. The dependence of MSAC lifetime on the vibrational quantum number, ν, is discussed for several regimes of V. Time-dependent perturbation theory yields lifetimes that deviate by ≲30% from non-perturbative results, over the range of V and ν studied, while a semi-classical model based on Landau–Zener tunneling is up to a factor of twenty off. The results are relevant to numerous atomic and molecular systems with metastable states on intersecting, coupled potential energy curves.

DOI
10.1088/1367-2630/ac6ca2

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Abstract Avoided crossings of level pairs with opposite slopes can form potential-energy minima for the external degree of freedom of quantum particles, giving rise to metastable states on the avoided crossings (MSACs). Nonadiabatic decay of MSACs is studied by solving the two-component Schrödinger equation in diabatic and adiabatic representations. Non-perturbative lifetime values are found by evaluating wave function flux and scattering phases of time-independent solutions, as well as wave-function decay of time-dependent solutions. The values from these methods generally agree well, validating the utilized approaches. As the adiabaticity parameter, V, of the system is increased by about a factor of ten across the mixed diabatic/adiabatic regime, the MSAC character transitions from marginally to highly stable, with the lifetimes increasing by about ten orders of magnitude. The dependence of MSAC lifetime on the vibrational quantum number, ν, is discussed for several regimes of V. Time-dependent perturbation theory yields lifetimes that deviate by ≲30% from non-perturbative results, over the range of V and ν studied, while a semi-classical model based on Landau–Zener tunneling is up to a factor of twenty off. The results are relevant to numerous atomic and molecular systems with metastable states on intersecting, coupled potential energy curves.
They have analytically tested several quantum transitions in molecular dynamics. In addition, they have introduced applications of theoretical formalism in physics to economics. First, they have completed the semiclassical theory of nonadiabatic transitions in the exponential potential model. They treated a two-state quantum system, which commonly appears as a subsystem in many-state problems. They were concerned with one-dimensional Schroedinger equation, although the type or semiclassical approach which they used can be applied to higher-dimension potential surfaces by means of Fourier transform. In particular, they solved the case of repulsive exponentially growing potentials, that is the forward-back scattering. They re-expressed the nonadiabatic transition matrix, which describes the transition between the two states for one-direction passage, in terms of contour integrals in the complex coordinate plane. 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This enables them to separate the whole coordinate region into distinct subsets and to analyze the physics in each subset separately. Applying this approach, they obtained a fully algebraic problem, which can be treated e.g. by diagrammatic techniques. Let them also mention that the complete transmission or complete reflection conditions simplify the wave function, and hence the mathematical solution. The formalism which they used while deriving the semiclassical conditions for the resonant phenomena mentioned above can be further generalized. This will probably yield a whole spectrum of tools in the laser control of molecular processes. Fourth, they developed a powerful technique for solving integral equations with singular kernel. One of the physical formulations of scattering is the time-independent approach based on the Lippmann-Schwinger equation for the Green operator. They have developed a detailed technique how to treat the singularity in this equation. 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The formalism above was proved to be extremely efficient taking the example of dissociative recombination H2+ + e- → H + H* because this is a diatomic system, quantum chemical data are easily available in the literature and they could demonstrate the superiority of their approach to the other approaches. Fifth, they suggested applications of basic physical concepts to economics. They introduced aggregate quantities in financial markets and interpreted these quantities as potential energy surfaces. They also formalized interactions between cyclic processes in terms of state to state transitions. Summarizing, they treated the exponential potential model of nonadiabatic transitions, introduced a new exactly solvable model of diabatically avoided crossing, discussed the semiclassical conditions for complete transmission and complete reflection from the viewpoint of laser control, contributed to scattering calculations, and introduced some interdisciplinary applications.
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We investigate the Landau–Zener (LZ) like dynamics of decaying two- and three-level systems with decay rates Γ 1 and Γ 2 for levels with minimum and maximum spin projection. Non-adiabatic and adiabatic transition probabilities are calculated from diabatic and adiabatic bases for two- and three-level systems. We extend the familiar two-level model of atoms with decay from the excited state out of the system into the hierarchy of three-level models which can be solved analytically or computationally in a non-perturbative manner. Exact analytical solutions are obtained within the framework of an extended form of the proposed procedure which enables to take into account all possible initial moments rather than large negative time t 0 = − ∞ as in standard LZ problems. We elucidate the applications of our results from a unified theoretical basis that numerically analyzes the dynamics of a system as probed by experiments.
We derive an exact solution of an explicitly time-dependent multichannel model of quantum mechanical nonadiabatic transitions. Our model corresponds to the case of a single linear diabatic energy level interacting with a band of an arbitrary N states, for which the diabatic energies decay with time according to the Coulomb law. We show that the time-dependent Schrödinger equation for this system can be solved in terms of Meijer functions whose asymptotics at a large time can be compactly written in terms of elementary functions that depend on the roots of an N th order characteristic polynomial. Our model can be considered a generalization of the Demkov–Osherov model. In comparison to the latter, our model allows one to explore the role of curvature of the band levels and diabatic avoided crossings.