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International Journal of Quantum Chemistry

On the applicability of a nonlinear Schrödinger equation to the determination of rate constants in Kramers' theory of chemical reactions

Dieter Schuch

Published Jan 1, 1993• 0 citations
Publisher

Abstract

Abstract In 1940, Kramers derived an expression for the rate constant of chemical reactions in viscous media. In this theory, chemical reactions are modeled as Brownian processes in the presence of potential barriers. The derivation of the rate constant is based on the solution of the Smoluchowski equation, a Fokker–Planck‐type equation in position space. Kramers' theory has been confirmed for reactions in systems ranging from nuclear processes to biochemical problems. The reaction rate can be obtained from the diffusion currents appearing in the Smoluchowski equation. A Smoluchowski‐type equation in position space, similar to the one applied by Kramers, has been used to find a nonlinear Schrödinger equation (NLSE) for dissipative, frictionally damped systems, taking into account wave‐particle duality. For several potentials, the NLSE can be solved exactly, and analytic expressions for the currents, appearing in the Smoluchowski equation and necessary to determine the rate constants, can be obtained. These currents are not only stationary, but can also be time‐dependent. It will be shown that, essentially, the determination of the time‐dependence of the currents can be reduced to the solution of Newton‐type equations of motion. © 1993 John Wiley & Sons, Inc.

DOI
10.1002/qua.560450302

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International Journal of Quantum Chemistry•Jan 1, 1999•29 citations
Abstract In 1940, Kramers derived an expression for the rate constant of chemical reactions in viscous media. In this theory, chemical reactions are modeled as Brownian processes in the presence of potential barriers. The derivation of the rate constant is based on the solution of the Smoluchowski equation, a Fokker–Planck‐type equation in position space. Kramers' theory has been confirmed for reactions in systems ranging from nuclear processes to biochemical problems. The reaction rate can be obtained from the diffusion currents appearing in the Smoluchowski equation. A Smoluchowski‐type equation in position space, similar to the one applied by Kramers, has been used to find a nonlinear Schrödinger equation (NLSE) for dissipative, frictionally damped systems, taking into account wave‐particle duality. For several potentials, the NLSE can be solved exactly, and analytic expressions for the currents, appearing in the Smoluchowski equation and necessary to determine the rate constants, can be obtained. These currents are not only stationary, but can also be time‐dependent. It will be shown that, essentially, the determination of the time‐dependence of the currents can be reduced to the solution of Newton‐type equations of motion. © 1993 John Wiley & Sons, Inc.
A new theory for the description of dissipative systems by nonlinear Schrödinger-type field equations (NLSE’s) with logarithmic nonlinearity, which has been recently developed by the authors, is applied to investigate the frictionally damped free motion and similar spatially unrestricted aperiodic problems. Wave-packet solutions as well as time-dependent wave-function solutions are derived and discussed. In the limit of vanishing friction (friction constant γ→0) these solutions turn into the well-known solutions of the respective linear Schrödinger field equation. The same applies to the mean values of position, momentum, and energy, as well as to the uncertainty product of position and momentum. For γ≠0, however, interesting new effects appear. In contrast to the linear theory the uncertainty product of position and momentum does not diverge any more for infinitely long times, t→∞, but asymptotically approaches a definite constant value which depends on characteristic parameters of the system like its mass, initial width, and friction constant γ. Another effect, the faster spreading of the Gaussian wave-packet solution compared to the linear theory, can be explained with the help of a special property of our nonlinear differential equation. In a way similar to what is usually only known for linear differential equations, the wave-packet solutions of our NLSE can be obtained by superposition of the wave functions which are individually also solutions of the same NLSE. The properties of the time-dependent superposition coefficients appearing in this connection are discussed. The extension to the corresponding three-dimensional problem as well as the differences arising in the investigation of the NLSE’s of the free fall and the motion in a constant electric field are given. Concluding, some differences are discussed which appear applying our nonlinear field theory to describe periodic or aperiodic motions, respectively.
In wave mechanics an appropriate description of a system under the influence of a linearly velocity dependent frictional force can be given by a nonlinear Schrödinger equation (NLSE) with logarithmic nonlinearity. However, the particular logarithmic form of the dissipative nonlinear frictional term in the NLSE is connected with the definition of the momentum- or velocity-operator in position-space. Therefore, in momentum-space, this form of the NLSE is no longer correct to describe the same physical sitution. This can be seen, e.g., from the fact that, in contrast to the linear case, the Fourier transform of the solution of the NLSE in position-space does not fulfill anymore the logarithmic NLSE in momentum-space. It will be shown, using results obtained from the theory in position-space, that it is possible to find a form of the nonlinear dissipative frictional term which is valid in position- as well as in momentum-space. Using this form, the NLSE looks like a diffusion equation with complex diffusion coefficient, i.e., a combination of a diffusion and a Schrödinger equation. The solution of this NLSE in momentum-space will be discussed. © 1994 John Wiley & Sons, Inc.
Abstract With the aid of a method similar to the one we used in an earlier work (part I) a new Schrödinger‐type field equation with logarithmic nonlinearity can be derived from a Fokker–Planck equation for a distribution function. This nonlinear field equation describes the frictinally damped motion of a system under the influence of a magnetic field and can be interpreted in the same way as the nonlinear Schrödinger‐type equation (NLSE) derived in part I, where no magnetic fields were taken into account. The NLSE for the two‐dimensional motion of a charged material system in a homogeneous magnetic field is solved exactly. The solutions are compared with the quantum‐mechanical solutions of the corresponding undamped problem. The method is extended to include also anisotropic conditions; i.e., in the Fokker–Plank equation the diffusion constant has to be replaced by a diffusion matrix, as different diffusion constants may be possible for different space directions. We regard the three‐dimensional motion under the combined influence of magnetic and electric fields according to K = (q/c)(v × B) + qE − mγv with Ey = (m/q)ω y, Ez = −(m/q)ω z, B = (0, 0, B) as an example. This is an approximation of the conditions existing in an ion cyclotron resonance spectrometry cell, neglecting an additional drift motion in the x direction which could be taken into account by Galilean transformation and gauge transformation. The corresponding NLSE for the coupled three‐dimensional motion is specified and solved exactly.
Taking into account wave-particle duality and the uncertainty principle, a nonlinear Schrödinger wave equation (NLSE) for the description of dissipative systems can be constructed by applying only Newton's form of classical mechanics. A comparison between our NLSE for dissipative systems and the linear time-dependent SE for conservative systems shows that, for free motion and motion in a harmonic potential, both equations have Gaussian wave-packet solutions. The time dependence of the maximum of these functions is governed by the classical (real) Newtonian equation of motion. While the time dependence of the width of the wave packet can be determined from a nonlinear complex Bernoulli/Ricatti type differential equation. This can be done by transformation into a Newton-type equation for a real quantity α (which is proportional to the square root of the width), including a kind of “centrifugal force” term. This equation can be solved analytically and when taken with Newton's equation of motion for the mean value of the position, it forms a so-called Ermakov system. For the linear SE equation, this implies the existence of a dynamical invariant. For our NLSE we also obtain such an exact invariant, but now for a dissipative system. Furthermore, this complex nonlinear equation can be linearised using the logarithmic derivative of a complex quantity λ, thus yielding a complex Newtonian equation of motion. The absolute value of λ is equivalent to α, the phase angle can be determined using a relation that connects real and imaginary parts of λ. This relation is linked to a kind of “conservation of angular momentum” for the quantity λ in a complex plane. The relations between the above-mentioned quantities will be discussed in detail.
The quantum Brownian motion of a particle in an external potential V(x) is treated using the master equation for the Wigner distribution function W(x, p, t) in phase space (x, p). A heuristic method of determination of diffusion coefficients in the master equation is proposed. The time evolution equation so obtained contains explicit quantum correction terms up to o(4) and in the classical limit, → 0, reduces to the Klein–Kramers equation. For a quantum oscillator, the method yields an evolution equation for W(x, p, t) coinciding with that of Agarwal (1971 Phys. Rev. A 4 739). In the non-inertial regime, by applying the Brinkman expansion of the momentum distribution in Weber functions (Brinkman 1956 Physica 22 29), the corresponding semiclassical Smoluchowski equation is derived.
Chemical reactions are generally connected with energy transfer between reactands and their environment. There are different ways of taking this environment into account. The traditional system-plus-reservoir (S+R) approach couples the relevant system to a large number of environmental degrees of freedom, represented, e.g., by harmonic oscillators. However, this has the disadvantage—from a computational point of view—that a system of many coupled differential equations has to be solved due to the large number of degrees of freedom of the reservoir. The number of degrees of freedom can be drastically reduced if an effective description of the interaction between system and reservoir is applied. On the quantum mechanical level, the effect of the environment can be included, e.g., by the use of explicitly time-dependent Hamiltonians or nonlinear additions to the Schrödinger equation (SE). An advantage of the former method is the preservation of the canonical formalism and the linearity of the theory as well as the fact that its operators can be derived directly from the S+R approach. Therefore, it seems to be even more of a paradox that this method apparently violates the uncertainty principle. This violation does not occur in the nonlinear approaches but the nonlinearity seems, at first sight, to be problematic. However, it can be shown that a particular logarithmic nonlinear SE is equivalent to the approach using the time-dependent Hamiltonian and can be transformed into this. The fact that this transformation is nonunitary provides the key for the solution of the paradox and also allows one to show the equivalence of all three of the above-mentioned approaches. In investigating the classical counterpart, a noncanonical transformation is used between the dissipative physical level and the canonical formal level, which makes it even possible to transform the physical interacting system into a formal isolated system that can be treated in the conventional way. As a result, the effect of the interaction with the environment can be taken into account classically by noncanonical transformations and quantum mechanically by nonunitary transformations. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 537–547, 1999