Non-monotonous short-time decay of the Loschmidt echo in quasi-one-dimensional systems

We study the short-time stability of quantum dynamics in quasi-one-dimensional systems with respect to small localized perturbations of the potential. To this end, we address, analytically and numerically, the decay of the Loschmidt echo (LE) during times short compared to the Ehrenfest time. We find that the LE is generally a non-monotonous function of time and exhibits strongly pronounced minima and maxima at the instants of time when the corresponding classical particle traverses the perturbation region. We also show that, under general conditions, the envelope decay of the LE is well approximated by a Gaussian, and we derive explicit analytical formulas for the corresponding decay time. Finally, we demonstrate that the observed non-monotonicity of the LE decay is only pertinent to one-dimensional (and, more generally, quasi-one-dimensional systems), and that the short-time decay of the LE can be monotonous in higher number of dimensions

Diffraction in time: An exactly solvable model

In recent years, matter-wave interferometry has attracted growing attention due to its unique suitability for high-precision measurements and the study of fundamental aspects of quantum theory. Diffraction and interference of matter waves can be observed not only at a spatial aperture (such as a screen edge, slit, or grating), but also at a time-domain aperture (such as an absorbing barrier, or “shutter,” that is being periodically switched on and off). The wave phenomenon of the latter type is commonly referred to as “diffraction in time.” Here, we introduce a versatile, exactly solvable model of diffraction in time. It describes time evolution of an arbitrary initial quantum state in the presence of a time-dependent absorbing barrier, governed by an arbitrary aperture function. Our results enable a quantitative description of diffraction and interference patterns in a large variety of setups, and may be used to devise new diffraction and interference experiments with atoms and molecules

Nonparametric estimation of multivariate convex-transformed densities

We study estimation of multivariate densities $p$ of the form $p(x)=h(g(x))$ for $x\in \mathbb {R}^d$ and for a fixed monotone function $h$ and an unknown convex function $g$. The canonical example is $h(y)=e^{-y}$ for $y\in \mathbb {R}$; in this case, the resulting class of densities [\mathcal {P}(e^{-y})={p=\exp(-g):g is convex}] is well known as the class of log-concave densities. Other functions $h$ allow for classes of densities with heavier tails than the log-concave class. We first investigate when the maximum likelihood estimator $\hat{p}$ exists for the class $\mathcal {P}(h)$ for various choices of monotone transformations $h$, including decreasing and increasing functions $h$. The resulting models for increasing transformations $h$ extend the classes of log-convex densities studied previously in the econometrics literature, corresponding to $h(y)=\exp(y)$. We then establish consistency of the maximum likelihood estimator for fairly general functions $h$, including the log-concave class $\mathcal {P}(e^{-y})$ and many others. In a final section, we provide asymptotic minimax lower bounds for the estimation of $p$ and its vector of derivatives at a fixed point $x_0$ under natural smoothness hypotheses on $h$ and $g$. The proofs rely heavily on results from convex analysis.Comment: Published in at http://dx.doi.org/10.1214/10-AOS840 the Annals of Statistics (http://www.imstat.org/aos/) by the Institute of Mathematical Statistics (http://www.imstat.org

Lyapunov spreading of semi-classical wave packets for the Lorentz Gas: theory and applications

We consider the quantum mechanical propagator for a particle moving in a $d$-dimensional Lorentz gas, with fixed, hard sphere scatterers. To evaluate this propagator in the semi-classical region, and for times less than the Ehrenfest time, we express its effect on an initial Gaussian wave packet in terms of quantities analogous to those used to describe the exponential separation of trajectories in the classical version of this system. This result relates the spread of the wave packet to the rate of separation of classical trajectories, characterized by positive Lyapunov exponents. We consider applications of these results, first to illustrate the behavior of the wave-packet auto-correlation functions for wave packets on periodic orbits. The auto-correlation function can be related to the fidelity, or Loschmidt echo, for the special case that the perturbation is a small change in the mass of the particle. An exact expression for the fidelity, appropriate for this perturbation, leads to an analytical result valid over very long time intervals, inversely proportional to the size of the mass perturbation. For such perturbations, we then calculate the long-time echo for semi-classical wave packets on periodic orbits. This paper also corrects an earlier calculation for a quantum echo, included in a previous version of this paper. We explain the reasons for this correction

The Quantum Normal Form Approach to Reactive Scattering: The Cumulative Reaction Probability for Collinear Exchange Reactions

The quantum normal form approach to quantum transition state theory is used to compute the cumulative reaction probability for collinear exchange reactions. It is shown that for heavy atom systems like the nitrogen exchange reaction the quantum normal form approach gives excellent results and has major computational benefits over full reactive scattering approaches. For light atom systems like the hydrogen exchange reaction however the quantum normal approach is shown to give only poor results. This failure is attributed to the importance of tunnelling trajectories in light atom reactions that are not captured by the quantum normal form as indicated by the only very slow convergence of the quantum normal form for such systems.Comment: 8 pages, 4 figure

Cycloaddition Chemistry of a Silylene‐Nickel Complex toward Organic π‐Systems: From Reversibility to C−H Activation

The versatile cycloaddition chemistry of the Si−Ni multiple bond in the acyclic (amido)(chloro)silylene→Ni0 complex 1, [(TMSL)ClSi→Ni(NHC)2] (TMSL=N(SiMe3)Dipp; Dipp=2,6‐iPr2C6H4; NHC=C[(iPr)NC(Me)]2), toward unsaturated organic substrates is reported, which is both reminiscent of and expanding on the reactivity patterns of classical Fischer and Schrock carbene–metal complexes. Thus, 1:1 reaction of 1 with aldehydes, imines, alkynes, and even alkenes proceed to yield [2+2] cycloaddition products, leading to a range of four‐membered metallasilacycles. This cycloaddition is in fact reversible for ethylene, whereas addition of an excess of this olefin leads to quantitative sp2‐CH bond activation, via a 1‐nickela‐4‐silacyclohexane intermediate. These results have been supported by DFT calculations giving insights into key mechanistic aspects.DFG, 390540038, EXC 2008: UniSysCatTU Berlin, Open-Access-Mittel - 202

Imputation Estimators Partially Correct for Model Misspecification

Inference problems with incomplete observations often aim at estimating population properties of unobserved quantities. One simple way to accomplish this estimation is to impute the unobserved quantities of interest at the individual level and then take an empirical average of the imputed values. We show that this simple imputation estimator can provide partial protection against model misspecification. We illustrate imputation estimators' robustness to model specification on three examples: mixture model-based clustering, estimation of genotype frequencies in population genetics, and estimation of Markovian evolutionary distances. In the final example, using a representative model misspecification, we demonstrate that in non-degenerate cases, the imputation estimator dominates the plug-in estimate asymptotically. We conclude by outlining a Bayesian implementation of the imputation-based estimation.Comment: major rewrite, beta-binomial example removed, model based clustering is added to the mixture model example, Bayesian approach is now illustrated with the genetics exampl

Origin of the exponential decay of the Loschmidt echo in integrable systems

We address the time decay of the Loschmidt echo, measuring the sensitivity of quantum dynamics to small Hamiltonian perturbations, in one-dimensional integrable systems. Using a semiclassical analysis, we show that the Loschmidt echo may exhibit a well-pronounced regime of exponential decay, similar to the one typically observed in quantum systems whose dynamics is chaotic in the classical limit. We derive an explicit formula for the exponential decay rate in terms of the spectral properties of the unperturbed and perturbed Hamilton operators and the initial state. In particular, we show that the decay rate, unlike in the case of the chaotic dynamics, is directly proportional to the strength of the Hamiltonian perturbation. Finally, we compare our analytical predictions against the results of a numerical computation of the Loschmidt echo for a quantum particle moving inside a one-dimensional box with Dirichlet-Robin boundary conditions, and find the two in good agreement