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Physical Review A

Nonadiabatic dynamics: Transitions between asymptotically degenerate states

Vladimir I. Osherov, Hiroki Nakamura

Published Apr 16, 2001• 3 citations
Publisher

Abstract

Nonadiabatic transitions between asymptotically degenerate potential curves are discussed. Both crossing and noncrossing two-coupled-Morse-potential systems are studied semiclassically as well as quantum mechanically. Conditions for the appearance of a nonadiabatic transition are clarified. The case of inverse power potentials at infinity is also analyzed. Expressions of nonadiabatic transition probability are obtained.

DOI
10.1103/physreva.63.052710

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The Journal of Chemical Physics•Nov 15, 1977•123 citations
Nonadiabatic transitions between asymptotically degenerate potential curves are discussed. Both crossing and noncrossing two-coupled-Morse-potential systems are studied semiclassically as well as quantum mechanically. Conditions for the appearance of a nonadiabatic transition are clarified. The case of inverse power potentials at infinity is also analyzed. Expressions of nonadiabatic transition probability are obtained.
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. The integrands are adiabatic momenta derived from the eigenvalues of potential matrix. Such type of concept has the advantage that it can be applied to other models than just the exponential potential model. Based on this, they have obtained an analytical tool for describing one-transition point class of potential curve systems. Examples are Rosen-Zener-Demkov model and Landau-Zener-Stueckelberg model. The formalism, which they contributed to, is useful in describing physical processes such as the charge transfer, and it is suitable for shaping external fields or modulating their frequencies in order to achieve a desired state or a product with the theoretical 100% probability. Second, they have derived the first exact analytical solution for a diabatically avoided crossing model. The physical system is described with one-dimensional coupled potential well and barrier which do not intersect in the whole coordinate range. On the basis of special mathematical functions they derived the complete quantum mechanical solution for the wave functions and the transmission coefficient. They also analyzed this model semiclassically and compared it with the exact results. This comparison yields interesting implications on the validity and accuracy of semiclassical approximation. In particular, they solved the case of dramatically avoided crossing with exponentially steep potential curves, and obtained the probability of one-way passage through the interaction region. The overall behavior corresponds to the probability of tunneling through the single potential barrier. In addition, there are complete reflection resonances at discrete energies, resulting from the trapping of a wave in the potential well. The formalism of diabatically avoided crossing model is useful in laser control of molecular reactions. This is because the potential energy curves in realistic molecular systems can be shifted by the photon energy; the curves are coupled by the field intensity via the dipole moment. That is why the new topology of potential energy curves, which was so far broadly omitted, becomes practically interesting due to the development in lasers techniques. Third, they treated several two-state quantum systems common in molecular physics. The semiclassical conditions for the complete transmission and the complete reflection in one-dimensional scattering were given analytically. They discovered the possibility of these phenomena in energy ranges in which the complete reflection or the complete transmission are not commonly expected to occur. In particular, they have made use of the broadly shared assumption that the transitions between the states are localized phenomena. 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. In particular, any scattering problem can be divided into two parts. The first one is the geometry of the system and the static interaction of its components. The second one is more dynamical: the singular equation for the Green operator including the variable energy of the scattering. They fix the most costly calculations in the static part. Then they solve the singularity analytically and thus obtain the cross section as a function of energy. The so far common approach is quite opposite: to fix the singularity first and then to recalculate heavily all the static part for any new value of energy. Obviously, their approach saves a considerable amount of computational time; therefore it is a good standpoint for treating large systems. 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.
Dynamics based on quantum trajectories with approximate quantum potential is generalized to nonadiabatic systems and its semiclassical properties are discussed. The formulation uses the mixed polar-coordinate space representation of a wave function. The polar part describes the overall time evolution of the wave-function components semiclassically using the single-surface approximate quantum potential. The coordinate part represents a complex``population'' amplitude, which in case of localized coupling can be solved for quantum mechanically in an efficient manner. In the high-energy regime this is accomplished by using a small basis determined by the coupling between surfaces. An illustration is given for a typical curve-crossing problem. The energy-resolved probabilities obtained from the time evolution of two wave packets for a wide range of energies are in excellent agreement with exact results for energies above the threshold of the diabatic reaction, including the case of total nonadiabatic transition.
The nonstationary Schr\"odinger equation is considered in a finite basis of states. The model Hamiltonian matrix corresponds to a single diabatic potential curve with a Coulombic $\ensuremath{\sim}1/t$ time dependence. An arbitrary number of other diabatic potential curves are flat, i.e., time independent and have arbitrary energies. Related states are coupled by constant interactions with the Coulomb state. The resulting nonstationary Schr\"odinger equation is solved by the method of contour integral. Probabilities of transitions to any other state are obtained as $\stackrel{\ensuremath{\rightarrow}}{t}\ensuremath{\infty}$ in a simple analytical form for the case when the Coulomb state is populated initially (at instant of time $\stackrel{\ensuremath{\rightarrow}}{t}+0).$ The formulas apply both to the cases when a horizontal diabatic potential curve is crossed by the Coulomb one and to a noncrossing situation. In the limit of weak coupling, the transition probabilities are interpreted in terms of a sequence of pairwise Landau-Zener-type transitions. Mapping of the Coulomb model onto an exactly solvable exponential multistate model is established. For the special two-state case, the well-known Nikitin model is recovered.
Nonsemiclassical effects in two-state and multistate curve crossing are considered. In the two-state case such effects appear in the crossing of nonlinear potentials and in systems described by nonlinear equations. Multistate curve crossing in linear potential grids involving two sets of parallel potentials is considered here using a quasidegeneracy approximation. The approximation describes phenomena, such as counterintuitive transitions and saturation (incomplete population transfer), not predictable by the assumption of independent crossings. Also, a new kind of oscillations due to quantum interference (different from the well-known Stückelberg oscillations) is disclosed, and its nature discussed.
This paper is concerned with the problem of calculating amplitudes for nonadiabatic transitions induced by a time-dependent Hamiltonian, in the semiclassical limit h/→0, with emphasis on questions relevant to semiclassical theories of electronically inelastic scattering. For this problem the semiclassical limit is mathematically equivalent to the adiabatic limit, and the adiabatic theorem says that all these transition amplitudes vanish in the limit; the question is, what is the asymptotic form of the nonadiabatic amplitudes, as they go to zero? We consider Hamiltonia that are analytic matrix functions of time. We prove a generalization of the adiabatic theorem to the complex time plane; paradoxically, the adiabatic theorem in the complex plane gives us directly the nonadiabatic amplitudes along the real time axis. We derive Dykhne’s remarkable formula for the two-state case, which says that the limiting form of the transition amplitude depends only on the energy curves of the two states, not on the nonadiabatic coupling which is responsible for transition between them. We discuss the three-state problem at length and show that the obvious generalization of the Dykhne formula is sometimes true, sometimes false. To indicate the scope of methods based on the adiabatic theorem in the complex plane, we give an elementary proof of the semiclassical formula for above-barrier reflection of a one-dimensional particle.