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The Journal of Chemical Physics

Two-state linear curve crossing problems revisited. IV. The best analytical formulas for scattering matrices

Chaoyuan Zhu, Hiroki Nakamura

Published Sep 15, 1994• 66 citations
Publisher

Abstract

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.

DOI
10.1063/1.468505

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Complete solutions of the Landau-Zener-Stueckelberg curve crossing problems, and their generalizations and applications

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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.

AIP conference proceedings•Jan 1, 2000•2 citations

Analytical Treatment of Some Quantum Transitions in Molecular Dynamic Processes

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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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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. 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Abstract Three analytic solutions to the Schrödinger equation for the time-dependent Landau–Zener (LZ) Hamiltonian are presented. They correspond to specific finite-time driving paths in a bounded parameter space of a two-level system. Two of these paths go through the avoided crossing of levels, either with a constant speed or with variable speed that decreases in the region of reduced energy gap, the third path bypasses the crossing such that the energy gap remains constant. The solutions yield exact time dependencies of the excitation probability for the system evolving from the ground state of the initial Hamiltonian. The LZ formula emerges as an approximation valid within a certain interval of driving times for the constant-speed driving through the avoided crossing. For long driving times, all solutions converge to the prediction of the adiabatic perturbation theory. The excitation probability vanishes at some discrete time instants.

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Yōsuke Kayanuma

The transition rate P ∞ in the level crossing with energy fluctuation is investigated numerically by the Wiener-Hermite expansion technique for the stochastic variable. It is shown that the fluctuation tends to modify the transition rate as if the nonadiabaticity is effectively increased and that the values of the Landau-Zener formula \(P_{\text{LZ}} \equiv 1 - \exp (-2 \pi J^{2}/\hbar |v|)\) and the strong damping formula \(P_{\text{SD}} \equiv \{1 - \exp (-4 \pi J^{2}/\hbar |v|)\}/2\) give the upper and the lower bounds of P ∞ , respectively, for given values of J 2 /| v |, where J is the off-diagonal coupling constant and v is the velocity of the change of the mean energy difference.

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Landau-Zener problem with decay and dephasing

Y. Avishai, Y. B. Band

Two aspects of the classic two-level Landau-Zener (LZ) problem are considered. First, we address the LZ problem when one or both levels decay, i.e., ${\ensuremath{\varepsilon}}_{j}(t)\ensuremath{\rightarrow}{\ensuremath{\varepsilon}}_{j}(t)\ensuremath{-}i{\ensuremath{\Gamma}}_{j}/2$. We find that if the system evolves from an initial time $\ensuremath{-}T$ to a final time $+T$ such that $|{\ensuremath{\varepsilon}}_{1}(\ifmmode\pm\else\textpm\fi{}T)\ensuremath{-}{\ensuremath{\varepsilon}}_{2}(\ifmmode\pm\else\textpm\fi{}T)|$ is not too large, the LZ survival probability of a state $|j\ensuremath{\rangle}$ can increase with increasing decay rate of the other state $|i\ensuremath{\ne}j\ensuremath{\rangle}$. This surprising result occurs because the decay results in crossing of the two eigenvalues of the instantaneous non-Hermitian Hamiltonian. On the other hand, if $|{\ensuremath{\varepsilon}}_{1}(\ifmmode\pm\else\textpm\fi{}T)\ensuremath{-}{\ensuremath{\varepsilon}}_{2}(\ifmmode\pm\else\textpm\fi{}T)|\ensuremath{\rightarrow}\ensuremath{\infty}$ as $T\ensuremath{\rightarrow}\ensuremath{\infty}$, the probability is independent of the decay rate. These results are based on analytic solutions of the time-dependent Schr\"odinger equations for two cases: (a) the energy levels depend linearly on time, and (b) the energy levels are bounded and of the form ${\ensuremath{\varepsilon}}_{1,2}(t)=\ifmmode\pm\else\textpm\fi{}\ensuremath{\varepsilon}tanh(t/\mathcal{T})$. Second, we study LZ transitions affected by dephasing by formulating the Landau-Zener problem with noise in terms of a Schr\"odinger-Langevin stochastic coupled set of differential equations. The LZ survival probability then becomes a random variable whose probability distribution is shown to behave very differently for long and short dephasing times. We also discuss the combined effects of decay and dephasing on the LZ probability.

arXiv:1311.3919•Physical Review A•Sep 30, 2014•22 citations
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.
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.
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 examine a previously overlooked aspect of the well-known Landau-Zener (LZ) problem, namely, the behavior in the intermediate, i.e., close to a crossing point, energy region, when all four LZ states are coupled and should be taken into account. We calculate the 4×4 connection matrix in this intermediate energy region, possessing the same block structure as the known connection matrices for the tunneling and in the over-barrier regions of the energy and continuously matching those in the corresponding energy regions. Applications of the results may concern various systems of physics, chemistry, or biology, ranging from molecular magnets and glasses to Bose condensed atomic gases.
Abstract Three analytic solutions to the Schrödinger equation for the time-dependent Landau–Zener (LZ) Hamiltonian are presented. They correspond to specific finite-time driving paths in a bounded parameter space of a two-level system. Two of these paths go through the avoided crossing of levels, either with a constant speed or with variable speed that decreases in the region of reduced energy gap, the third path bypasses the crossing such that the energy gap remains constant. The solutions yield exact time dependencies of the excitation probability for the system evolving from the ground state of the initial Hamiltonian. The LZ formula emerges as an approximation valid within a certain interval of driving times for the constant-speed driving through the avoided crossing. For long driving times, all solutions converge to the prediction of the adiabatic perturbation theory. The excitation probability vanishes at some discrete time instants.
The transition rate P ∞ in the level crossing with energy fluctuation is investigated numerically by the Wiener-Hermite expansion technique for the stochastic variable. It is shown that the fluctuation tends to modify the transition rate as if the nonadiabaticity is effectively increased and that the values of the Landau-Zener formula PLZ≡1−exp⁡(−2πJ2/ℏ∣v∣)P_{\text{LZ}} \equiv 1 - \exp (-2 \pi J^{2}/\hbar |v|)PLZ​≡1−exp(−2πJ2/ℏ∣v∣) and the strong damping formula PSD≡{1−exp⁡(−4πJ2/ℏ∣v∣)}/2P_{\text{SD}} \equiv \{1 - \exp (-4 \pi J^{2}/\hbar |v|)\}/2PSD​≡{1−exp(−4πJ2/ℏ∣v∣)}/2 give the upper and the lower bounds of P ∞ , respectively, for given values of J 2 /| v |, where J is the off-diagonal coupling constant and v is the velocity of the change of the mean energy difference.
Two aspects of the classic two-level Landau-Zener (LZ) problem are considered. First, we address the LZ problem when one or both levels decay, i.e., ${\ensuremath{\varepsilon}}_{j}(t)\ensuremath{\rightarrow}{\ensuremath{\varepsilon}}_{j}(t)\ensuremath{-}i{\ensuremath{\Gamma}}_{j}/2$. We find that if the system evolves from an initial time $\ensuremath{-}T$ to a final time +T+T+T such that $|{\ensuremath{\varepsilon}}_{1}(\ifmmode\pm\else\textpm\fi{}T)\ensuremath{-}{\ensuremath{\varepsilon}}_{2}(\ifmmode\pm\else\textpm\fi{}T)|$ is not too large, the LZ survival probability of a state $|j\ensuremath{\rangle}$ can increase with increasing decay rate of the other state $|i\ensuremath{\ne}j\ensuremath{\rangle}$. This surprising result occurs because the decay results in crossing of the two eigenvalues of the instantaneous non-Hermitian Hamiltonian. On the other hand, if $|{\ensuremath{\varepsilon}}_{1}(\ifmmode\pm\else\textpm\fi{}T)\ensuremath{-}{\ensuremath{\varepsilon}}_{2}(\ifmmode\pm\else\textpm\fi{}T)|\ensuremath{\rightarrow}\ensuremath{\infty}$ as $T\ensuremath{\rightarrow}\ensuremath{\infty}$, the probability is independent of the decay rate. These results are based on analytic solutions of the time-dependent Schr\"odinger equations for two cases: (a) the energy levels depend linearly on time, and (b) the energy levels are bounded and of the form ${\ensuremath{\varepsilon}}_{1,2}(t)=\ifmmode\pm\else\textpm\fi{}\ensuremath{\varepsilon}tanh(t/\mathcal{T})$. Second, we study LZ transitions affected by dephasing by formulating the Landau-Zener problem with noise in terms of a Schr\"odinger-Langevin stochastic coupled set of differential equations. The LZ survival probability then becomes a random variable whose probability distribution is shown to behave very differently for long and short dephasing times. We also discuss the combined effects of decay and dephasing on the LZ probability.