Fitting elephants in the density functionals zoo: Statistical criteria for the evaluation of density functional theory methods as a suitable replacement for counting parameters

Counting parameters has become customary in the density functional theory community as a way to infer the transferability of popular approximations to the exchange‐correlation functionals. Recent work in data science, however, has demonstrated that the number of parameters of a fitted model is not related to the complexity of the model itself, nor to its eventual overfitting. Using similar arguments, here, we show that it is possible to represent every modern exchange‐correlation functional approximations using just one single parameter. This procedure proves the futility of the number of parameters as a measure of transferability. To counteract this shortcoming, we introduce and analyze the performance of three statistical criteria for the evaluation of the transferability of exchange‐correlation functionals. The three criteria are called Akaike information criterion, Vapnik‐Chervonenkis criterion, and cross‐validation criterion and are used in a preliminary assessment to rank 60 exchange‐correlation functional approximations using the ASCDB database of chemical data.     

Optimum step-stress accelerated degradation test for Wiener degradation process under constraints

To assess a product's reliability for subsequent managerial decisions such as designing an extended warranty policy and developing a maintenance schedule, Accelerated Degradation Test (ADT) has been used to obtain reliability information in a timely manner. In particular, Step-Stress ADT (SSADT) is one of the most commonly used stress loadings for shortening test duration and reducing the required sample size. Although it was demonstrated in many previous studies that the optimum SSADT plan is actually a simple SSADT plan using only two stress levels, most of these results were obtained numerically on a case-by-case basis. In this paper, we formally prove that, under the Wiener degradation model with a drift parameter being a linear function of the (transformed) stress level, a multi-level SSADT plan will degenerate to a simple SSADT plan under many commonly used optimization criteria and some practical constraints. We also show that, under our model assumptions, any SSADT plan with more than two distinct stress levels cannot be optimal. These results are useful for searching for an optimum SSADT plan, since one needs to focus only on simple SSADTs. A numerical example is presented to compare the efficiency of the proposed optimum simple SSADT plans and a SSADT plan proposed by a previous study. In addition, a simulation study is conducted for investigating the efficiency of the proposed SSADT plans when the sample size is small.     

Is it worthwhile to go beyond the local-density approximation in subsystem density functional theory?

Frozen density embedding (FDE) theory is one of the major techniques aiming to bring modeling of extended chemical systems into the realm of high accuracy calculations. To improve its accuracy it is of interest to develop kinetic energy density functional approximations specifically for FDE applications. In the study reported here we focused on optimizing parameters of a generalized gradient approximation-like kinetic energy functional with the purpose of better describing electron excitation energies. We found that our optimized parametrizations, named excPBE and excPBE-3 (as these are derived from a Perdew-Burke-Ernzerhof-like parametrization), could not yield improvements over available functionals when applied on a test set of systems designed to probe solvatochromic shifts. Moreover, as several different functionals yielded very similar errors to the simple local-density approximation (LDA), it is questionable whether it is worthwhile to go beyond the LDA in this context.     

Density Functional Theory as a Data Science

The development of density functional theory (DFT) functionals and physical corrections are reviewed focusing on the physical meanings and the semiempirical parameters from the viewpoint of data science. This review shows that DFT exchange‐correlation functionals have been developed under many strict physical conditions with minimizing the number of the semiempirical parameters, except for some recent functionals. Major physical corrections for exchange‐correlation function‐ als are also shown to have clear physical meanings independent of the functionals, though they inevitably require minimum semiempirical parameters dependent on the functionals combined. We, therefore, interpret that DFT functionals with physical corrections are the most sophisticated target functions that are physically legitimated, even from the viewpoint of data science.     

相伴随机变量序列的泛函型几乎处处中心极限定理

对于均值为零的平稳相伴随机变量序列,首先证明了在L(n)=EX_1~2 2 sum from n to j=2 Cov(X_1,X_j)是一个缓变函数的条件下的泛函型几乎处处中心极限定理.另外还给出了正则化部分和函数的对数平均几乎处处收敛性.     

Non-anticipative representations of Banach space valued gaussian processes with respect to brownian motion

Necessary and sufficient conditions are found for the equivalence of the measures associated with (i) a Banach space valued Gaussian process, with mean 0, and (ii) a Bach space valued Brownian motion. The notion of a non-anticipative representation of (i) with respect to (ii) is defined and in the case of equivalence of the measures it is shown that such a representation exists and has an explicit stochastic integral form which is invertible. Theorems of Ershov on absolute continuity of measures associated with diffusion processes are extended to Banach space. Applications to infinite-dimensional filtering are considered.     

采用(meta)-GGA泛函对Ag(111)、Rh(111)和Ir(111)上乙烯吸附的理论研究

本文针对在多种催化反应的重要中间体乙烯,使用(meta)-GGA等级的包含PBE,BEEF-vdW,SCAN以及SCAN+rVV10在内的多种交换关联泛函,系统研究了在过渡金属表面(Ag,Rh和Ir)上乙烯吸附势能面对泛函的依赖关系. 研究发现,对于乙烯在贵金属Ag(111)上的吸附,除了PBE外,BEEF-vdW,SCAN以及SCAN+rVV10均能预测出物理吸附态的存在. 对于乙烯在Rh(111)面的吸附,SCAN和SCAN+rVV10预测在化学吸附位之前存在有物理吸附前驱态,而基于PBE和BEEF-vdW的势能面并没有发现前驱态的存在. 而对于乙烯在Ir(111)上的吸附,BEEF-vdW也能微弱地预测出化学吸附前驱态的存在. 研究结果表明,无论在哪一种金属表面上,四种泛函中SCAN+rVV10给出的吸附能最强,其次是SCAN,最后是PBE或者BEEF-vdW.     

Determining the role of the underlying orbital‐dependence of PBE0‐DH and PBE‐QIDH double‐hybrid density functionals

We study the orbital‐dependence of three (parameter‐free) double‐hybrid density functionals, namely the PBE0‐DH, the PBE‐QIDH models, and the SOS1‐PBE‐QIDH spin‐opposite‐scaled variant of the latter. To do it, we feed all their energy terms with different sets of orbitals obtained previously from self‐consistent density functional theory calculations using several exchange‐correlation functionals (e.g., PBE, PBE0, PBEH&H), or directly with HF‐PBE orbitals, to see their effect on selected datasets for atomization and reaction energies, the latter proned to marked self‐interaction errors. We find that the PBE‐QIDH double‐hybrid model shows a great consistency, as the best results are always obtained for the set of orbitals corresponding to its hybrid scheme, which prompts us to recommend this model without any other fitting or reparameterization. © 2017 Wiley Periodicals, Inc.     

Exact Rates of Convergence of Functional Limit Theorems for Csörgő;-Révész Increments of a Wiener Process

Let {W(t); t≥ 0} be a standard Wiener process and S be the Strassen set of functions. We investigate the exact rates of convergence to zero (as T→∞) of the variables $ \sup _{{0 \leqslant t \leqslant T - \alpha _{T} }} \inf _{{f \in S}} \sup _{{0 \leqslant x \leqslant 1}} {\left| {Y_{{t,T}} {\left( x \right)} - f{\left( x \right)}} \right|} Let {W(t); t≥ 0} be a standard Wiener process and S be the Strassen set of functions. We investigate the exact rates of convergence to zero (as T→∞) of the variables sup_{0≤ t ≤ T − aT} inf _f∈S sup_{0≤ x ≤1}|Y _t,T (x) −f(x)| and inf_{0≤ t ≤ T−aT} sup_{0≤ x ≤1}|Y _t,T (x−f(x)| for any given f∈S, where Y _t,T (x) = (W(t+xa _T ) −W(t)) (2a _T (log Ta _T ⁻¹ + log log T))^−1/2. We establish a relation between how small the increments are and the functional limit results of Cs?rg{\H o}-Révész increments for a Wiener process. Similar results for partial sums of i.i.d. random variables are also given. Received September 10, 1999, Accepted June 1, 2000     

The Wiener transform on the Besicovitch spaces

In his fundamental research on generalized harmonic analysis, Wiener proved that the integrated Fourier transform defined by is an isometry from a nonlinear space of functions of bounded average quadratic power into a nonlinear space of functions of bounded quadratic variation. We consider this Wiener transform on the larger, linear, Besicovitch spaces defined by the norm . We prove that maps continuously into the homogeneous Besov space for and , and is a topological isomorphism when .