Direct Ensemble Estimation of Density Functionals

Estimating density functionals of analog sources is an important problem in statistical signal processing and information theory. Traditionally, estimating these quantities requires either making parametric assumptions about the underlying distributions or using non-parametric density estimation followed by integration. In this paper we introduce a direct nonparametric approach which bypasses the need for density estimation by using the error rates of k-NN classifiers asdata-driven basis functions that can be combined to estimate a range of density functionals. However, this method is subject to a non-trivial bias that dramatically slows the rate of convergence in higher dimensions. To overcome this limitation, we develop an ensemble method for estimating the value of the basis function which, under some minor constraints on the smoothness of the underlying distributions, achieves the parametric rate of convergence regardless of data dimension.Comment: 5 page

Nonparametric estimation of infinitely divisible distributions based on variational analysis on measures

The paper develops new methods of non-parametric estimation a compound Poisson distribution. Such a problem arise, in particular, in the inference of a Levy process recorded at equidistant time intervals. Our key estimator is based on series decomposition of functionals of a measure and relies on the steepest descent technique recently developed in variational analysis of measures. Simulation studies demonstrate applicability domain of our methods and how they positively compare and complement the existing techniques. They are particularly suited for discrete compounding distributions, not necessarily concentrated on a grid nor on the positive or negative semi-axis. They also give good results for continuous distributions provided an appropriate smoothing is used for the obtained atomic measure

On Bayesian based adaptive confidence sets for linear functionals

We consider the problem of constructing Bayesian based confidence sets for linear functionals in the inverse Gaussian white noise model. We work with a scale of Gaussian priors indexed by a regularity hyper-parameter and apply the data-driven (slightly modified) marginal likelihood empirical Bayes method for the choice of this hyper-parameter. We show by theory and simulations that the credible sets constructed by this method have sub-optimal behaviour in general. However, by assuming "self-similarity" the credible sets have rate-adaptive size and optimal coverage. As an application of these results we construct $L_{\infty}$-credible bands for the true functional parameter with adaptive size and optimal coverage under self-similarity constraint.Comment: 11 pages, 2 figure

Sieve Inference on Semi-nonparametric Time Series Models

The method of sieves has been widely used in estimating semiparametric and nonparametric models. In this paper, we first provide a general theory on the asymptotic normality of plug-in sieve M estimators of possibly irregular functionals of semi/nonparametric time series models. Next, we establish a surprising result that the asymptotic variances of plug-in sieve M estimators of irregular (i.e., slower than root-T estimable) functionals do not depend on temporal dependence. Nevertheless, ignoring the temporal dependence in small samples may not lead to accurate inference. We then propose an easy-to-compute and more accurate inference procedure based on a "pre-asymptotic" sieve variance estimator that captures temporal dependence. We construct a "pre-asymptotic" Wald statistic using an orthonormal series long run variance (OS-LRV) estimator. For sieve M estimators of both regular (i.e., root-T estimable) and irregular functionals, a scaled "pre-asymptotic" Wald statistic is asymptotically F distributed when the series number of terms in the OS-LRV estimator is held fixed. Simulations indicate that our scaled "pre-asymptotic" Wald test with F critical values has more accurate size in finite samples than the usual Wald test with chi-square critical values.Weak dependence, Sieve M estimation, Sieve Riesz representor, Irregular functional, Misspecification, Pre-asymptotic variance, Orthogonal series long run variance estimation, F distribution

Electronic Spectra from TDDFT and Machine Learning in Chemical Space

Due to its favorable computational efficiency time-dependent (TD) density functional theory (DFT) enables the prediction of electronic spectra in a high-throughput manner across chemical space. Its predictions, however, can be quite inaccurate. We resolve this issue with machine learning models trained on deviations of reference second-order approximate coupled-cluster singles and doubles (CC2) spectra from TDDFT counterparts, or even from DFT gap. We applied this approach to low-lying singlet-singlet vertical electronic spectra of over 20 thousand synthetically feasible small organic molecules with up to eight CONF atoms. The prediction errors decay monotonously as a function of training set size. For a training set of 10 thousand molecules, CC2 excitation energies can be reproduced to within $\pm$0.1 eV for the remaining molecules. Analysis of our spectral database via chromophore counting suggests that even higher accuracies can be achieved. Based on the evidence collected, we discuss open challenges associated with data-driven modeling of high-lying spectra, and transition intensities

Fluctuation theorems for stochastic dynamics

Fluctuation theorems make use of time reversal to make predictions about entropy production in many-body systems far from thermal equilibrium. Here we review the wide variety of distinct, but interconnected, relations that have been derived and investigated theoretically and experimentally. Significantly, we demonstrate, in the context of Markovian stochastic dynamics, how these different fluctuation theorems arise from a simple fundamental time-reversal symmetry of a certain class of observables. Appealing to the notion of Gibbs entropy allows for a microscopic definition of entropy production in terms of these observables. We work with the master equation approach, which leads to a mathematically straightforward proof and provides direct insight into the probabilistic meaning of the quantities involved. Finally, we point to some experiments that elucidate the practical significance of fluctuation relations.Comment: 48 pages, 2 figures. v2: minor changes for consistency with published versio