The compact analytical complete solutions recently obtained for the two-state Landau-Zener-Stueckelberg problems are reviewed and explained. The theory covers both Landau-Zener (LZ) type in which the two diabatic potential curves cross with the same sign of slopes and the nonadiabatic tunneling (NT) type in which the potentials cross with different signs of slopes. The theory is applicable virtually in the whole range of energy and coupling strength and is convenient for practical use. The new theory for time-dependent nonadiabatic transition can be formulated from the time-independent theory of the LZ-type. The utilizability of the theory to various multi-channel problems and also to multi-dimensional problems is demonstrated and explained. The intriguing phenomenon of complete reflection which appears in the NT-case is explicitly utilized to propose a new type of molecular switching and to control molecular processes such as molecular photodissociation. Also proposed is a new way of controlling molecular processes by using time-dependent external fields. Finally, a trial to formulate a unified analytical theory to cover both Landau-Zener-Stueckelberg and Rosen-Zener-Demkov types of nonadiabatic transitions is briefly touched upon.
The compact analytical complete solutions recently obtained for the two-state Landau-Zener-Stueckelberg problems are reviewed and explained. The theory covers both Landau-Zener (LZ) type in which the two diabatic potential curves cross with the same sign of slopes and the nonadiabatic tunneling (NT) type in which the potentials cross with different signs of slopes. The theory is applicable virtually in the whole range of energy and coupling strength and is convenient for practical use. The new theory for time-dependent nonadiabatic transition can be formulated from the time-independent theory of the LZ-type. The utilizability of the theory to various multi-channel problems and also to multi-dimensional problems is demonstrated and explained. The intriguing phenomenon of complete reflection which appears in the NT-case is explicitly utilized to propose a new type of molecular switching and to control molecular processes such as molecular photodissociation. Also proposed is a new way of controlling molecular processes by using time-dependent external fields. Finally, a trial to formulate a unified analytical theory to cover both Landau-Zener-Stueckelberg and Rosen-Zener-Demkov types of nonadiabatic transitions is briefly touched upon.
Based on the achievements of the previous three papers of this series, the best working formulas for scattering matrix are obtained for both the Landau–Zener (LZ) and the nonadiabatic tunneling (NT) case: two formulas valid at b2≥0 and b2≤0 in the LZ case, and three formulas valid atb2≤−1, −1≤b2≤1 and b2≥1 in the NT case, where b2 represents the effective energy. Simple and compact formulas which work far better than the LZ formula are proposed for nonadiabatic transition probability by one passage of crossing point for both the LZ and NT cases. Furthermore, compact expressions are derived, for the first time, for the nonadiabatic tunneling probability at b2≤1, i.e., at energies lower than the bottom of the upper adiabatic potential. All the formulas proposed here can be usefully utilized at any coupling strength, namely the validity range has been very much expanded compared to the previous formulas by employing certain empirical corrections. Besides, these formulas have convenience to enable an extension to general curved potentials.
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.
The WKB analysis for higher order differential equations had not been developed until recent progress of the so-called exact WKB method, so it was difficult to find WKB solutions for multistate nonadiabatic models in general, whereas enormous efforts were made especially for the study of generalized Landau-Zener models. Under such circumstances Aoki-Kawai-Takei provided a closed expression for the S matrix of a time-dependent multistate nonadiabatic system, in which diabatic potential curves are given as polynomial functions of time and they all intersect with each other. Their result is completely explicit, and the model covers much wider classes of systems than multistate nonadiabatic models studied so far. Here we numerically show how their exact WKB formula works as long as crossing points of diabatic potential curves are well separated. The model studied includes the cases where diabatic potential functions are nonlinear, not like generalized Landau-Zener models. We also discuss the situations where virtual turning points and new Stokes curves, new components in the Stokes geometry appearing only for higher order differential equations, come into play. In particular, we examine how the presence of new Stokes curves affects final transition probabilities using a couple of concrete examples.
The two-state Stueckelberg-Landau-Zener theory of curve crossings can be utilized to explain qualitatively many of the observed asymmetric-inelastic total cross sections. It predicts not only a broad maximum in the inelastic total cross sections as a function of velocity, but also a rapid rise to this maximum followed by a slow decline past the maximum. If the difference in the potentials between the two states possesses an extremum, oscillations superimposed upon the general velocity dependence of the inelastic total cross sections may also be expected because of the existence of a stationary phase. At high velocities, the spacing of these oscillations will be proportional to ${v}^{\ensuremath{-}1}$.
It is pointed out that there exists an interesting strong and weak duality in the Landau-Zener-Stueckelberg potential curve crossing. A reliable perturbation theory can thus be formulated in the both limits of weak and strong interactions. It is shown that main characteristics of the potential crossing phenomena such as the Landau-Zener formula including its numerical coefficient are well-described by simple (time-independent) perturbation theory without referring to Stokes phenomena. A kink-like topological object appears in the ``magnetic'' picture, which is responsible for the absence of the coupling constant in the prefactor of the Landau-Zener formula. It is also shown that quantum coherence in a double well potential is generally suppressed by the effect of potential curve crossing, which is analogous to the effect of Ohmic dissipation on quantum coherence.
A field-dependent su(2) gauge transformation connects between the adiabatic and diabatic pictures in the (Landau-Zener-Stueckelberg) potential curve crossing. It is pointed out that weak and strong potential curve crossing interactions are interchanged under this transformation, thus realizing a naive strong and weak duality. A reliable perturbation theory should thus be formulated in limits of both weak and strong interactions. In fact, the main characteristics of the potential crossing phenomena such as the Landau-Zener formula including its numerical coefficient are well described by simple (time-independent) perturbation theory without referring to Stokes phenomena. We also show that quantum coherence in a double-well potential is generally suppressed by the effect of a potential curve crossing, which is analogous to the effect of Ohmic dissipation on quantum coherence.