A semiclassical solution of general two-state non-adiabatic transition and tunneling is found analytically within the Wentzel–Kramers–Brillouin (WKB) semiclassical framework associated with the Stokes phenomenon in mathematics. The non-adiabatic scattering matrix is determined by a complex quantity called the Stokes constant, which can be directly connected to the complex transition points of the WKB solution. An accurate and compact analytical solution is found for this Stokes constant which is a function of three parameters, one of which corresponds to the diabatic-to-adiabatic transformation angle that is interpreted as a type of non-adiabatic transition. Numerical examples demonstrate that the present unified analytical semiclassical theory works very well for both non-adiabatic transition and non-adiabatic tunneling. The present analytical semiclassical method can be a very powerful tool for application to multidimensional non-adiabatic dynamic processes.
A semiclassical solution of general two-state non-adiabatic transition and tunneling is found analytically within the Wentzel–Kramers–Brillouin (WKB) semiclassical framework associated with the Stokes phenomenon in mathematics. The non-adiabatic scattering matrix is determined by a complex quantity called the Stokes constant, which can be directly connected to the complex transition points of the WKB solution. An accurate and compact analytical solution is found for this Stokes constant which is a function of three parameters, one of which corresponds to the diabatic-to-adiabatic transformation angle that is interpreted as a type of non-adiabatic transition. Numerical examples demonstrate that the present unified analytical semiclassical theory works very well for both non-adiabatic transition and non-adiabatic tunneling. The present analytical semiclassical method can be a very powerful tool for application to multidimensional non-adiabatic dynamic processes.
A general Wentzel–Kramers–Brillouin (WKB) theory of multidimensional tunneling is formulated and an illuminating physical picture of the effects of multidimensionality is provided. Two basic problems are solved: (i) Maslov’s semiclassical wave function in the classically accessible region is connected to the wave function in the classically inaccessible region and (ii) the latter is propagated into the deep tunneling region. It is found that there exist two distinct types of tunneling: pure tunneling and mixed tunneling. The former is the usual one in which the tunneling path can be defined by a certain classical trajectory on the inverted potential and its associated action is pure imaginary. In the latter case, no tunneling path can be defined and the Huygens-type wave propagation should be carried out. In this case, tunneling is always accompanied by classical motion in the transversal direction and the associated action is complex. A general procedure is presented for the evaluation of energy splitting ΔE in the double well. Moreover, under the locally separable linear approximation, a simple and convenient formula for ΔE is derived and is confirmed to work well by comparison with the exact numerical calculations.
The semiclassical approximation, particularly the Wentzel-Kramers-Brillouin (WKB) method, has been a cornerstone in quantum mechanics for understanding systems where quantum effects are present but allow for an approximate classical description. Despite its widespread success in providing intuitive insights into phenomena like tunneling and energy quantization, the standard WKB expansion often suffers from asymptotic divergence and limited accuracy, especially for lower quantum numbers or near turning points. This paper introduces a novel approach to enhance the precision and convergence of the WKB method by integrating variational principles with advanced resummation techniques. We propose a framework where the WKB expansion for key physical quantities is treated as an asymptotic series, and its coefficients are optimized through a variational procedure derived from the underlying quantum dynamics. Subsequently, these optimized series are subjected to resummation methods, such as generalized Borel transforms or Padé approximants, to extract highly accurate and convergent results. Our methodology aims to transcend the limitations of conventional WKB by systematically incorporating non-perturbative information and improving the analytic properties of the semiclassical series. We present the theoretical foundations of this "Resummed Variational WKB" approach, outlining its potential to yield unprecedented precision in calculating energy eigenvalues, tunneling rates, and other quantum observables, thereby bridging the gap between purely classical and fully quantum mechanical descriptions with enhanced quantitative fidelity.
The WKB method is commonly used in semiclassical approximations to the wave function in both the classically allowed and the forbidden regions of a one-dimensional potential. In a multidimensional space, the method can be adapted to construct wave functions in an ``allowed'' region from classical trajectories or wave normals. However, in the ``forbidden'' region the WKB wave function is in general specified by two sets of wave fronts, the equiphase and the equiamplitude surfaces or equivalently by two sets of paths defined to be normal to these surfaces, respectively. We present a Huygens-type construction for obtaining these wave fronts and paths, which reveals that for non-normal incidence the paths are coupled to each other. The analysis enables us to answer some of the basic questions concerning tunneling in multidimensional nonseparable potentials. A special and important case occurs when the incident wave is normal to the turning surface. We show that for normal incidence the path equations are decoupled and are equivalent to Newton's equations of motion for the inverted potential and energy.
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.
We apply a many-body Wentzel-Kramers-Brillouin (WKB) approach to determine the leading quantum corrections to the semiclassical dynamics of the Josephson model, describing interacting bosons able to tunnel between two localized states. The semiclassical dynamics is known to divide between regular oscillations and self-trapped oscillations where the sign of the imbalance remains fixed. In both cases, the WKB wave functions are matched to Airy functions, yielding a modified Bohr-Sommerfeld quantization condition. At the critical energy dividing normal and self-trapped oscillations, the WKB wave functions should instead be matched to parabolic cylinder functions, leading to a quantization formula that is not just the Bohr-Sommerfeld formula, and recovering the known logarithmic quantum break times at this energy. This work thus provides another illustration of the usefulness of the WKB approach in certain many-body problems.
The mutual consistency and structural interconnection between the Wentzel-Kramers-Brillouin (WKB) and Wigner-Kirkwood (WK) semiclassical approximations is investigated for nonrelativistic N-particle systems, with mutual scalar interactions and coupling to an external time-varying electromagnetic field. The generalized WK expansion of the propagator 〈x\ensuremath{\Vert}U(t,s)\ensuremath{\Vert}y〉 is obtained from a large-mass expansion of the higher-order WKB approximation. Two techniques are described for computing the WK coefficient functions. One relies on a large-mass expansion of classical paths and the transport representation of the WKB approximation; the other is recursive in nature. For time-independent Hamiltonians H the standard WK expansion of the heat kernel 〈x\ensuremath{\Vert}${e}^{\mathrm{\ensuremath{-}}\ensuremath{\beta}H}$\ensuremath{\Vert}y〉 is recovered.