ABSTRACT In the last decade, the rapid evolution of ultrafast laser spectroscopy has provided new impetus to the branch of chemistry dealing with tunneling processes involving electrons and light atoms. The possibility of measuring the time required by a particle to cross a barrier opens new perspectives for understanding the kinetics and dynamics of tunneling processes. In this study, a model is developed to estimate the tunneling time in tautomerization reactions based on proton transfer through a classically forbidden barrier. The proposed approach uses the asymptotic values of the wavefunction to compute the dwell time, which is the average time spent by the proton inside the potential barrier. The theory is formulated for both static barriers, which are good approximations for isolated molecules, and dynamic barriers to account for the effects of the chemical bath. The model performance is evaluated by two numerical simulations, in which a proton is transferred via tunneling in a double‐well potential; the tunneling barrier is approximated by a static and dynamical rectangular potential. A possible extension of the theory to open systems is briefly discussed within the framework of the Caldeira–Leggett model.
ABSTRACT In the last decade, the rapid evolution of ultrafast laser spectroscopy has provided new impetus to the branch of chemistry dealing with tunneling processes involving electrons and light atoms. The possibility of measuring the time required by a particle to cross a barrier opens new perspectives for understanding the kinetics and dynamics of tunneling processes. In this study, a model is developed to estimate the tunneling time in tautomerization reactions based on proton transfer through a classically forbidden barrier. The proposed approach uses the asymptotic values of the wavefunction to compute the dwell time, which is the average time spent by the proton inside the potential barrier. The theory is formulated for both static barriers, which are good approximations for isolated molecules, and dynamic barriers to account for the effects of the chemical bath. The model performance is evaluated by two numerical simulations, in which a proton is transferred via tunneling in a double‐well potential; the tunneling barrier is approximated by a static and dynamical rectangular potential. A possible extension of the theory to open systems is briefly discussed within the framework of the Caldeira–Leggett model.
The concept of ‘tunnelling time’ in the context of quantum particle tunnelling is reviewed. Various suggestions of linking the tunnelling dynamics with a characteristic time (real or complex) like the phase time, barrier interaction time (bounce time), presence time, etc. are analysed. A simple but fully quantal method of defining and estimating a real tunnelling time is examined in a variety of situations. The recently proposed idea of interpreting ‘tunnelling time’ as the cavity lifetime of a particle is also explored. We emphasize that proton or H-atom transfer reactions in double or triple wells offer systems in which the signature of the tunnelling time should be recognizable not just indirectly through the tunnelling splitting of spectral lines, but by following the relaxation dynamics of the subsystem that the proton or H atom leaves by tunnelling.
Proton transfer plays a key role in the applications of advanced energy materials as well as in the functionalities of biological systems. In this work, based on the transfer matrix method, we study the quantum effects of proton transfer in a series of one-dimensional (1D) model potentials and numerically calculate the quantum probability of transferring across single and double barriers (wells). In the case of single barriers, when the incident energies of protons are above the barrier height, the quantum oscillations in the transmission coefficients depend on the geometric shape of the barriers. It is found that atomic resonant tunneling (ART) not only presents in the rectangular single well and rectangular double barriers as expected, but also exists in the other types of potential wells and double barriers. For hetero-structured double barriers, there is no resonant tunneling in the classical forbidden zone, i.e., in the case when the incident energy (E i) is lower than the barrier height (E b). Furthermore, we have provided generalized analysis on the characteristics of transmission coefficients of hetero-structured rectangular double barriers.
Introduction In classical physics it is meaningful to ask the question, ‘How much time does a particle take to pass through a given region?’ The interesting question in quantum mechanics is: does a particle take a definite time to tunnel through a classically forbidden region? The question has been debated ever since the idea that there was such a time in quantum theory was first put forward by MacColl way back in 1932 [253]. A plethora of times has since then been proposed, and the answer seems to depend on the interpretation of quantum mechanics one uses. A reliable answer is clearly of great importance for the design of high-frequency quantum devices, tunnelling phenomena (as, for example, in scanning tunneling microscopy), nuclear and chemical reactions and, of course, for purely conceptual reasons. Most of the controversies centre around simple and intuitive notions in idealized one-dimensional models in a scattering configuration in which a particle (usually represented by a wave packet) is incident on a potential barrier localized in the interval [ a, b ]. Three kinds of time have been defined in this context. One, called the transmission time τ T ( a, b ), is the average time spent within the barrier region by the particles that are eventually transmitted. Similarly, the reflection time τ R ( a, b ) is the average time spent within the barrier region by the particles that are eventually reflected.
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.