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CRC Press eBooks

Tunneling in Chemical Reactions

Hiroki Nakamura, Gennady Mil'nikov

Published Jul 18, 2013• 2 citations
Publisher

Abstract

In the case of tunneling in chemical reactions [see figure1.1(c)], the total energy of reagents cannot be generally considered to be small; treating it as the first-order term of h¯ as was successfully done in Chapters 6 and 7 does not lead to any sensible semiclassical theory. The semiclassical mechanics requires (1) construction of Lagrange manifolds, (2) determination of amultidimensional caustic surface, and (3) connection of wave functions between classically allowed and forbidden regions [59]. Unfortunately, these problems have not yet been solved mathematically. As was discussed in Section 3.1, in the framework of the ordinary WKB approach we can construct Lagrange manifolds and caustics in the case of two dimensions and the connection problem can be treated relatively well by assuming the local separability. Extension of this method to higher dimensions, however, cannot be practical. The complexvalued (complex coordinate and/or momentum) WKB theory has been devised, as briefly explained there, but cannot be simply extended to multidimensions (see, for instance, [15]). This formidable task can hardly be accomplished mainly because of the complexity of the Lagrange manifold and the fact that analytical properties of any realistic potential energy surfaces extended into the complex-valued coordinate space cannot be guaranteed. The use of a complex trajectory was nicely materialized by the double-ended complex trajectory in the classical S-matrix theory [206], in which the quantized boundary conditions are satisfied at both (initial and final) ends. Unfortunately, this method turned out not to be practically useful, because finding such trajectories is also a formidable task in a multidimensional complex coordinate (and/or momentum) space. We can, however, make a break through the difficulty of detecting caustics in multidimensional space. An efficient way of doing that has been devised along classical trajectory [47]. This is not a trivial task at all, since it is not possible to find caustics in high-dimensional space by just shooting classical trajectories. Since the caustics can be found along each classical trajectory, chemical dynamics with tunneling effects incorporated can now be treated by the on-the-fly method. In this subsection, this method is explained.

DOI
10.1201/b14673-13

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There are enormous amounts of literature dealing with quantum mechanical tunneling phenomena, andmanymonographs have also been published recently covering various fields of the phenomenon [21-24]. Unfortunately, however, theories of multidimensional tunneling phenomena are not yet satisfactorily developed. Effective numerical algorithms in quantum mechanics such as MCTDH (multichannel timedependent Hartree) method [25] and quantum Monte Carlo method [26] have been developed and successfully implemented to study quantum dynamics in multidimensional systems. However, exact quantum dynamics methods require a formidable task including accurate ab initio calculations of global potential energy surfaces. Besides, it is not straightforward to obtain the physical insights of dynamic processes.

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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.

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In the case of tunneling in chemical reactions [see figure1.1(c)], the total energy of reagents cannot be generally considered to be small; treating it as the first-order term of h¯ as was successfully done in Chapters 6 and 7 does not lead to any sensible semiclassical theory. The semiclassical mechanics requires (1) construction of Lagrange manifolds, (2) determination of amultidimensional caustic surface, and (3) connection of wave functions between classically allowed and forbidden regions [59]. Unfortunately, these problems have not yet been solved mathematically. As was discussed in Section 3.1, in the framework of the ordinary WKB approach we can construct Lagrange manifolds and caustics in the case of two dimensions and the connection problem can be treated relatively well by assuming the local separability. Extension of this method to higher dimensions, however, cannot be practical. The complexvalued (complex coordinate and/or momentum) WKB theory has been devised, as briefly explained there, but cannot be simply extended to multidimensions (see, for instance, [15]). This formidable task can hardly be accomplished mainly because of the complexity of the Lagrange manifold and the fact that analytical properties of any realistic potential energy surfaces extended into the complex-valued coordinate space cannot be guaranteed. The use of a complex trajectory was nicely materialized by the double-ended complex trajectory in the classical S-matrix theory [206], in which the quantized boundary conditions are satisfied at both (initial and final) ends. Unfortunately, this method turned out not to be practically useful, because finding such trajectories is also a formidable task in a multidimensional complex coordinate (and/or momentum) space. We can, however, make a break through the difficulty of detecting caustics in multidimensional space. An efficient way of doing that has been devised along classical trajectory [47]. This is not a trivial task at all, since it is not possible to find caustics in high-dimensional space by just shooting classical trajectories. Since the caustics can be found along each classical trajectory, chemical dynamics with tunneling effects incorporated can now be treated by the on-the-fly method. In this subsection, this method is explained.
Tunneling is a supreme quantum effect. Every introductory text [1] on quantum mechanics gives the paradigm example of a particle tunneling through a one-dimensional potential barrier despite having a total energy less than the barrier height. Indeed, the reader typically works through a number of exercises, all involving one-dimensional potential barriers of one form or another modeling several key physical phenomena ranging from atom transfer reactions to the decay of α-particles [2]. However, one seldom encounters coupled multidimenisonal tunneling in such texts since an analytical solution of the Schro¨dinger equation in such cases is not possible. Interestingly, the richness and complexity of the tunneling phenomenon manifest themselves in full glory in the case of multidimensional systems [3]. Thus, for instance, the usual one-dimensional expectation of increasing tunneling splittings as one approaches the barrier top from below is not necessarily true as soon as one couples another bound degree of freedom to the tunneling coordinate. In the context of molecular reaction dynamics, multidimensional tunneling can result in strong mode-specificity and fluctuations in the reaction rates [4]. In fact, a proper description of tunneling of electrons and hydrogen atoms is absolutely essential [5,6] even in molecular systems as large as enzymes and proteins. Although one usually assumes tunneling effects to be significant in molecules involving light atom transfers, it is worth pointing out that neglecting the tunneling of even a heavy atom like carbon is the difference between a reaction occurring or not occurring. In particular, one can underestimate rates by nearly hundred orders of magnitude [7]. Interestingly, and perhaps paradoxically, several penetrating insights into the nature and mechanism of multidimensional barrier tunneling have been obtained from a phase-space perspective [8,9]. The contributions by Creagh, Shudo and Ikeda, and Takahashi in the present volume provide a detailed account of the latest advances in the phasespace-based understanding of multidimensional barrier tunneling.
There are enormous amounts of literature dealing with quantum mechanical tunneling phenomena, andmanymonographs have also been published recently covering various fields of the phenomenon [21-24]. Unfortunately, however, theories of multidimensional tunneling phenomena are not yet satisfactorily developed. Effective numerical algorithms in quantum mechanics such as MCTDH (multichannel timedependent Hartree) method [25] and quantum Monte Carlo method [26] have been developed and successfully implemented to study quantum dynamics in multidimensional systems. However, exact quantum dynamics methods require a formidable task including accurate ab initio calculations of global potential energy surfaces. Besides, it is not straightforward to obtain the physical insights of dynamic processes.
A method that uses only real valued coordinates is presented for integrating the many dimensional semiclassical wave function into the forbidden region. The procedure first determines a surface of caustic points by running the set of trajectories that define the wave function in the allowed region. In the forbidden region, the momentum and the action integral are both complex functions of position, and their imaginary parts vanish on the caustic surface. The direction of the imaginary part of the momentum p(I) can be chosen to the perpendicular to the caustic surface at all points on that surface. Equations are derived for integrating the values of the real and imaginary parts of the momentum along the curves that follow the direction of p(I). The equations for the change in the action integral and the prefactor for the semiclassical wave function along these curves are also obtained, allowing for the determination of the semiclassical wave function in the forbidden region. Calculations are performed for a two dimensional problem, and the semiclassical wave function is found to be is excellent agreement with the results of exact quantum calculations.
It is rather obvious that one-dimensional theory is not good enough to comprehend quantum mechanical tunneling phenomena. For instance, the tunneling splitting estimated using the one-dimensional potential along the intrinsic reaction coordinate gives a few orders of magnitude smaller value [56]. There is a more crucial example that demonstrates the conceptual deficiency of one-dimensional treatment and shows interesting features peculiar to multidimensional tunneling phenomena. This is explained in Chapter 4. In this sense, multidimensional treatment is definitely needed. Herewe describe the two-dimensionalWKB theory developed by Takada and Nakamura [30].
We study a quantum theory in terms of action decomposed function (ADF), a class of quantum wave function, towards many-dimensional applications to quantum dynamics of heavy particles as in chemical reactions. The equation of motion for the complex-valued amplitude of ADF represents a coupling between the internal diffusive motion of a wave packet and dynamics of its group velocity in a hierarchical manner ascending from classical to purely quantum mechanics via semiclassical dynamics. We attempt to solve this equation of motion dividing it into two stages: a semiclassical level and beyond. In this paper, as the first stage, we develop a semiclassical approximation in the Lagrange picture of classical phase flow. In the Euler picture (as in the standard WKB picture), continuous integration of the stability matrix along the paths is required. By adopting the Lagrange picture, on the other hand, we represent the semiclassical amplitude in terms of what we call deviation determinant, which can be evaluated readily in many-dimensional systems. Numerical tests show that ADF reproduces quantum wave packets at each space-time point along classical paths very well. However, the ADF in this stage is not free of the semiclassical singularity. In other words, the wave functions diverge at turning points or caustics, depending on the initial conditions chosen. This divergence is known to take place at points where classical paths smoothly distributed in phase space have ``focuses'' in configuration space (or momentum space) and reflects an intrinsic relationship between quantum and classical mechanics. Therefore, it is by studying the mechanism of removing the singularity that the essential feature of quantum mechanics will be clarified. This aspect will be discussed in a companion paper [K. Takatsuka and S. Takahashi, Phys. Rev. A 89, 012109 (2014)] as the second stage of many-body quantum theory.
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.