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Ultrafast Science

Deciphering Quantum Tunneling Dynamics: Insights from Sub-Barrier Interactions and Complex Time Analysis

Xiwang Liu, Xiaokai Li, Yichong Lin, Shidong Yang, Ming Zhu, Xiaohong Song, Chuncheng Wang, Jing Chen, Weifeng Yang, Dajun Ding

Published Oct 13, 2025• 2 citations
Publisher

Abstract

Quantum tunneling, a quintessential quantum phenomenon, challenges classical intuitions by allowing particles to pass through seemingly insurmountable barriers. This study delves into the intricate dynamics of electron tunneling, focusing on the critical role of sub-barrier interactions and complex time processes. Through a combination of experimental measurements and simulations based on Feynman’s path integral of complex time trajectories, we reveal that the sub-barrier potential interaction introduces an asymmetric electron wave packet probability distribution along the real time axis and a marked delay at the tunneling exit. The energy-dependent behavior of this delay in electronic tunneling agrees with that observed in the previous atomic tunneling studies, suggesting a universal mechanism underlying quantum tunneling across different scales. Our findings underscore the necessity of incorporating both the wave and particle aspects of quantum entities to fully comprehend tunneling dynamics, which holds promise for an intuitive interpretation of complex-number quantum processes.

DOI
10.34133/ultrafastscience.0122

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Tunneling times and excited state interactions between chromophores

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This Thesis consists of two related parts. The first part (Chapters 2 and 3) presents the results of a fundamental theoretical study of the interpretation of quantum mechanics, and particularly of tunneling processes. Part two (Chapters 4, 5, and 6) describes the experimental results of spectroscopic investigations of quantum mechanical interactions between chromophores, which may play a role in electron transport by means of tunneling.The formulation of the quantum theory at the beginning of the twentieth century resulted in a scientific revolution. The impact of this theory on our physical world picture is still visible today. The quantum theory is impressively successful in its predictions of the outcomes of experiments, but the interpretation of the theory is still shaky. The predictions of quantum mechanics about the outcome of experiments are detailed and testable, but the meaning of the theory for quantum systems, in which no measurement has taken place is not clear. 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Recent results on electron tunneling across a potential barrier, inferred from observations or obtained from theoretical models, have suggested superluminal or instantaneous barrier traversal times. In this work we investigate relativistic wave-packet dynamics for an electron tunneling through a potential barrier employing space-time resolved solutions to relativistic quantum field theory (QFT) equations. We prove by linking the QFT property of microcausality to the wave-packet behavior that the tunneling dynamics is fully causal, precluding instantaneous or superluminal effects. We illustrate these results by performing numerical computations for an electron tunneling through a potential barrier for standard tunneling as well for Klein tunneling. In all cases (Klein tunneling or regular tunneling across a standard or a supercritical potential) the transmitted wave packet remains in the causal envelope of the propagator, even when its average position lies ahead of the average position of the corresponding freely propagated wave packet.

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Quantum tunneling, a quintessential quantum phenomenon, challenges classical intuitions by allowing particles to pass through seemingly insurmountable barriers. This study delves into the intricate dynamics of electron tunneling, focusing on the critical role of sub-barrier interactions and complex time processes. Through a combination of experimental measurements and simulations based on Feynman’s path integral of complex time trajectories, we reveal that the sub-barrier potential interaction introduces an asymmetric electron wave packet probability distribution along the real time axis and a marked delay at the tunneling exit. The energy-dependent behavior of this delay in electronic tunneling agrees with that observed in the previous atomic tunneling studies, suggesting a universal mechanism underlying quantum tunneling across different scales. Our findings underscore the necessity of incorporating both the wave and particle aspects of quantum entities to fully comprehend tunneling dynamics, which holds promise for an intuitive interpretation of complex-number quantum processes.
Tunnelling lies at the heart of quantum mechanics and is a fundamental process in attosecond science, molecular biology, and quantum devices. Whether tunnelling takes time and how a microscopic particle transits through a barrier have been debated since the early days of quantum mechanics. The time required for an electron to tunnel through an atomic potential barrier has been measured with attosecond angular streaking (attoclock), and a recent work on the hydrogen atom claimed that electron tunnelling is instantaneous. However, the time required for Rb atoms to tunnel through an optical potential barrier has been measured to be on the order of milliseconds with a recent Larmor clock measurement. The essence of electron and atom tunnelling is identical, but the reason for the contradictory conclusions remains unknown. Here, we demonstrate that the sub-barrier potential interaction is the root of the nonzero tunnelling delay time. We reveal that the wave-particle duality of a tunnelling electron must be fully taken into account when decoding the tunnelling delay time from the attoclock measurements. Based on energy-resolved attoclock measurements, we show that the tunnelling delay time of an electron ranges from 24 to 58 attoseconds, and the counterintuitive result that an electron with a lower energy may spend less time in the barrier is consistent with the velocity-dependent tunnelling time of atoms in Larmor clock measurements. Our results unify the tunnelling time of microscopic particles by highlighting the classically forbidden sub-barrier potential interactions of matter waves.
The wave-packet simulation (WPS) method for calculating the time a tunneling particle spends inside a one-dimensional potential barrier is reexamined using the Feynman path-integral technique. Following earlier work by Sokolovski and Baskin [Phys. Rev. A 36, 4604 (1987)], the tunneling (or traversal) time tpackT{\mathit{t}}_{\mathrm{pack}}^{\mathit{T}}tpackT​ is defined as a matrix element of a classical nonlocal functional between two states that represent the initial and transmitted wave packets. These states do not lie on the same orbit in Hilbert space; as a result, tpackT{\mathit{t}}_{\mathrm{pack}}^{\mathit{T}}tpackT​ is complex-valued. It is shown that RetpackT{\mathit{t}}_{\mathrm{pack}}^{\mathit{T}}tpackT​ reduces to the standard WPS result, tphaseT{\mathit{t}}_{\mathrm{phase}}^{\mathit{T}}tphaseT​, for conditions similar to those employed in the conventional WPS analysis. Similarly, ImtpackT{\mathit{t}}_{\mathrm{pack}}^{\mathit{T}}tpackT​ is shown to contain information about the energy dependence of the transmission probability. Under semiclassical conditions, ImtpackT{\mathit{t}}_{\mathrm{pack}}^{\mathit{T}}tpackT​ reduces to the well-known Wentzel-Kramers-Brillouin expression for the tunneling time. It is shown there are different definitions for the traversal time of a classical moving object, whose size is comparable to the width of the region of interest. In the quantum case, these different definitions correspond to different ways of analyzing the WPS experiment. The path-integral approach demonstrates that the tunneling-time problem is one of understanding the physical significance of complex-valued off-orbit matrix elements of an operator or functional. The physical content of complex-valued tunneling times is discussed. It is emphasized that the use of complex tunneling times includes real-time approaches as a special case. Nevertheless, there is a limitation in the description of tunneling experiments using tunneling times, whether real or complex. The path-integral approach does not supply a universal traversal time, analogous to a classical time, that can be used in quantum situations. It is demonstrated that the often expressed hope of finding a well-defined and universal real tunneling time is erroneous.
Quantum tunneling, as a quintessential quantum phenomenon, has been investigated in detail both theoretically and experimentally. Still, the physical picture of the tunneling process is not intuitive, leading to some confusion and paradoxes. In this paper, we have tried to gain insight into quantum tunneling by a phase-space approach. For this purpose, we scrutinize the evolution of the Wigner distribution during tunneling and derive the energy and momentum spectra by integrating over a segment of phase space. In this way, some of the difficulties and paradoxes in tunneling probability, energy conservation, and tunneling time are given a clearer interpretation. Negative probabilities in the Wigner distribution play a key role in the tunneling process, and the origin of negative probabilities clearly indicates that the volatility of matter underlies the various exotic phenomena involved.
This Thesis consists of two related parts. The first part (Chapters 2 and 3) presents the results of a fundamental theoretical study of the interpretation of quantum mechanics, and particularly of tunneling processes. Part two (Chapters 4, 5, and 6) describes the experimental results of spectroscopic investigations of quantum mechanical interactions between chromophores, which may play a role in electron transport by means of tunneling.The formulation of the quantum theory at the beginning of the twentieth century resulted in a scientific revolution. The impact of this theory on our physical world picture is still visible today. The quantum theory is impressively successful in its predictions of the outcomes of experiments, but the interpretation of the theory is still shaky. The predictions of quantum mechanics about the outcome of experiments are detailed and testable, but the meaning of the theory for quantum systems, in which no measurement has taken place is not clear. Various interpretations exist. Two of these are compared in Chapter 2. The first is the orthodox or Copenhagen interpretation, which was advocated by the Copenhagen-based Niels Bohr. His followers claimed that, in the orthodox interpretation, nothing can be said about the properties of systems if no suitable measurement has been carried out. The alternative is the causal interpretation of quantum mechanics, in which a particle, e.g. an electron, has a well-defined position and velocity at each instant of time independent of a measurement act. The causal theory does not assign a special role to the observer. In the causal interpretation the location as a function of time amounts to trajectories. The two interpretations are empirically equivalent, i.e. they predict the same experimental outcomes.In Chapter 2 the meaning of the two interpretations is clarified by the notion of tunneling time. Tunneling is the quantum mechanical phenomenon that a particle can cross a barrier even if its energy is less than the barrier energy. The time a particle takes to tunnel is the tunneling time. Time is a confusing concept: quantum theory appears not to know how to handle this topic. Time appears in the quantum mechanical formulae as a parameter, and not as an operator that corresponds to an observable quantity. Since an unambiguous time operator is missing, it is interesting to see what different interpretations have to say about tunneling times. It is strictly speaking impossible to define tunneling times in the orthodox interpretation because of the lack of a clear time operator, of which the expectation value can be observed by experiment. In the causal interpretation, every trajectory corresponds to a possible path of an electron. The density functions determine the probability that particles move on particular trajectories. This is how the stochastic character of quantum mechanics is accounted for in this interpretation. The transmission time is defined as the time spent inside the barrier by the electrons that eventually cross the barrier. The average transmission time can be defined by means of the trajectories, both in the case of stationary wave functions and in that of time-dependent, Gaussian wave packets. The Gaussian wave packets travel from minus infinity to plus infinity. On the way they meet potential barriers, which cause them to be reflected or transmitted. The process by which an electron moves from one chromophore to another can be described as tunneling because of the high potential barrier formed by the medium between the chromophores. In this Thesis the experimental media used are polymer films and apolar solutions. The model described in Chapter 2 is generally used in the literature but appears not to be applicable for a system of two chromophores and a tunneling electron, because electrons belonging to chromophores neither start in infinity nor go to infinity. A better model, a double potential well, is used in Chapter 3. The conclusion of Chapter 2 is that the transmission time can be defined in the causal interpretation when time-dependent wave packets are used.Chapter 3 illustrates the preceding by tunneling of a particle from one potential well to another passing a potential barrier. This model is the so-called double potential well. Examples are primary charge separation in the photosynthetic reaction center and in artificial model systems of chromophores in solutions and polymer films. The latter two cases are investigated spectroscopically in this Thesis. In these molecular systems, effective electron transport between chromophores after absorption of light takes place, yielding charge separation, i.e. the formation of chromophore cations. During their transport between natural or artificial chromophores, the released electrons often have to pass weak conducting media, corresponding to high potential barriers. If the energy of the electron exceeds the energy of the potential barrier, electron transport can be explained by classical theories. However, if the energy of the electron falls below the energy of the potential barrier, this is no longer possible. The transport mechanism is then understood as quantum mechanical tunneling. Experimental proof of tunneling has been found at low temperatures in photosynthesis.In Chapter 3 the chromophores and the tunneling electrons are described by double potential wells. Each well represents a chromphore and the space between the molecules a potential barrier. The formalism of the causal interpretation is applied to define a transmission time. The transmission time can be found using trajectories. An alternative method provides the average transmission time without calculating the trajectories. Arrival time distribution functions are defined and these are used to determine the average arrival time of the tunneling electrons at the entrance and at the exit of the barrier. Because arrival time distribution functions and hence both average arrival times and transmission times are not determined in an experimental context, we conclude that these definitions of transmission times are meaningless in the orthodox interpretation. The question posed at the end of Chapter 3 is whether, and if so how, these transmission times are experimentally accessible.The theoretical models developed in Chapters 2 and 3 are too simple to be extrapolated to real systems, such as electron transport between an electron donor and an acceptor, one of which is excited by light. Intermolecular interactions between excited electron donor molecules and ground state surrounding molecules cannot be neglected in chromophore films and solutions with relatively high concentrations of chromophores. These excitonic interactions should be included in adequate descriptions of electron transfer. Chapters 4, 5, and 6 describe these interactions using absorption and emission spectroscopy. In Chapter 4 a theoretical description of the absorption characteristics of chromophores in disordered films is given. At low concentrations, chromophores in films are mainly monomers. On statistical grounds, however, we conclude that some molecules are close enough together to form dimer-like structures, concentration pairs with characteristic absorption spectra. The presence of these concentration pairs influences the emission characteristics of chromophore films as well. When monomer electrons are excited by the absorption of photons, the electrons might return to the ground state, giving off their energy as fluorescence. Light energy can also be transferred to neighboring concentration pairs, in which case the fluorescence is quenched.The aim of Chapter 4 is to estimate the influence of potential quenchers in the vicinity of excited monomers and to predict the influence of these quenchers on the absorption spectra. The transfer of energy from monomers to concentration pairs, the so-called Förster transfer, takes place over quite large distances (1-5 nm). Statistics can be used to calculate the number of quenchers in particular concentrations of chromophores. In the literature it is assumed that two monomers that form a concentration pair are randomly oriented with respect to each other. If these pairs consisted of randomly oriented monomers and all fluctuations are taken into account, it appears on theoretical grounds that there would not be enough quenchers to describe the experimental changes. Because most chromophores are elongated or pancake-like, they are not randomly oriented but exhibit preferential orientations. These preferential orientations increase the efficiency of fluorescence quenching and theory and experiment are thereby reconciled. An analytical expression of the spectral changes compared to monomeric spectra of randomly oriented dimers is presented. To describe the interaction between chromophores that have one dominant transition dipole moment, a point dipole exciton model is used. To enhance the description of the spectral changes, homogeneous and inhomogeneous line broadening and monomer-to- monomer distance fluctuations should be taken into account. Inclusion of these factors in the model gives rise to the conclusion that the dimer spectra are broadened compared to the monomeric spectra and that the broadening is stronger at the blue end than at the red end of the spectra. However, to detect the blue-shifted spectral profile of randomly oriented dime-like samples, the concentration needs to be so high that isolated dimers cannot be observed. Then, simulation of the dimers becomes impossible, and all mutual interactions must be taken into account. Modeling of these interactions shows that the blue shift is not visible, and that only a broadening of the absorption spectra with respect to the monomeric spectra remains.Chapter 5 describes spectral changes that result from changes in the concentration changes of elongated Erythrosin-B (Ery B) chromophores in polyvinylalcohol (PVA) films. At low concentrations, monomers ar
The time evolution of a quantum-mechanical tunnelling process is discussed. The use of a quantum generalization of particle paths facilitates the separation of particle and wave aspects of tunnelling. We present a novel complex time object which enters invariantly several tunnelling times derived for barriers of arbitrary shape. Its asymptotic behaviour is shown to agree with an intuitive understanding of particle tunnelling. As a result, the complementary features of several tunnelling times are identified exactly for the first time.
Recent results on electron tunneling across a potential barrier, inferred from observations or obtained from theoretical models, have suggested superluminal or instantaneous barrier traversal times. In this work we investigate relativistic wave-packet dynamics for an electron tunneling through a potential barrier employing space-time resolved solutions to relativistic quantum field theory (QFT) equations. We prove by linking the QFT property of microcausality to the wave-packet behavior that the tunneling dynamics is fully causal, precluding instantaneous or superluminal effects. We illustrate these results by performing numerical computations for an electron tunneling through a potential barrier for standard tunneling as well for Klein tunneling. In all cases (Klein tunneling or regular tunneling across a standard or a supercritical potential) the transmitted wave packet remains in the causal envelope of the propagator, even when its average position lies ahead of the average position of the corresponding freely propagated wave packet.