Chemometric Tools to Point Out Benchmarks and Chromophores in Pigments through Spectroscopic Data Analyses

Spectral preprocessing data and chemometric tools are analytical methods widely applied in several scientific contexts i.e., in archaeometric applications. A systematic classification of natural powdered pigments of organic and inorganic nature through Principal Component Analysis with a multi-instruments spectroscopic study is presented here. The methodology allows the access to elementary and molecular unique benchmarks to guide and speed up the identification of an unknown pigment and its recipe. This study is conducted on a set of 48 powdered pigments and tested on a real-case sample from the wall painting in S. Maria Delle Palate di Tusa (Messina, Italy). Four spectroscopic techniques (X-ray Fluorescence, Raman, Attenuated Total Reflectance and Total Reflectance Infrared Spectroscopies) and six different spectrometers are tested to evaluate the impact of different setups. The novelty of the work is to use a systematic approach on this initial dataset using the entire spectroscopic energy range without any windows selection to solve problems linked with the manipulation of large analytes/materials to find an indistinct property of one or more spectral bands opening new frontiers in the dataset spectroscopic analyses.     

A Range-Compaction Heuristic for Graph Coloring

This paper presents a novel heuristic for graph coloring that works on a range of colors and iteratively tries to make this range more compact. This range-compaction heuristic also has a pressure component and an annealing schedule for it. The value of this component is empirically quantified. This algorithm is evaluated on a wide range of DIMACS benchmark graphs, and found to be competitive with state-of-the-art algorithms in terms of solution quality and run time.     

Coloring graphs by iterated local search traversing feasible and infeasible solutions

Graph coloring is one of the hardest combinatorial optimization problems for which a wide variety of algorithms has been proposed over the last 30 years. The problem is as follows: given a graph one has to assign a label to each vertex such that no monochromatic edge appears and the number of different labels used is minimized. In this paper we present a new heuristic for this problem which works with two different functionalities. One is defined by two greedy subroutines, the former being a greedy constructive one and the other a greedy modification one. The other functionality is a perturbation subroutine, which can produce also infeasible colorings, and the ability is then to retrieve feasible solutions. In our experimentation the proper tuning of this optimization scheme produced good results on known graph coloring benchmarks.     

TD‐DFT benchmarks: A review

Time‐Dependent Density Functional Theory (TD‐DFT) has become the most widely‐used theoretical approach to simulate the optical properties of both organic and inorganic molecules. In this contribution, we review TD‐DFT benchmarks that have been performed during the last decade. The aim is often to pinpoint the most accurate or adequate exchange‐correlation functional(s). We present both the different strategies used to assess the functionals and the main results obtained in terms of accuracy. In particular, we discuss both vertical and adiabatic benchmarks and comparisons with both experimental and theoretical reference transition energies. More specific benchmarks (oscillator strengths, excited‐state geometries, dipole moments, vibronic shapes, etc.) are summarized as well. © 2013 Wiley Periodicals, Inc.     

Measuring the relative balance of DMUs

In basic Data Envelopment Analysis (DEA) models, the weights of performance criteria are endogenously determined, assigning to each decision-making unit (DMU) its best possible efficiency score. This property is widely considered to be a major strength of the method, but it is also a source of considerable problems concerning performance assessment and performance control. Such problems result from the possibility of zero-value weights that exclude criteria from the evaluation. Unlike approaches that deal with this issue by incorporating value judgments into the analysis, we suggest a complementary balance score that is derived from the given data set. This score evaluates the extent to which a DMU avoids concentration on only some of the crucial performance criteria. One of the possible decisions resulting from a balance analysis is to reduce the set of DMUs considered to serve as benchmarks. For this case, a modified CCR–O model is presented.     

钍基熔盐堆用238群中子-48群光子耦合多群常数库的屏蔽基准验证

采用OKTAVIAN脉冲球实验对钍基熔盐堆用AMPX主库格式238群中子-48群光子耦合多群常数库进行了屏蔽基准验证,重点检验了该库中的F,Li,Be,C、Al,Si,Cr,Ni,Zr,Co,Cu,Mn,Mo,Nb,Ti,W,Pb同位素/元素的数据。采用SCALE 5.1程序系统中的XSDRN-PM程序进行一维屏蔽问题计算,将计算结果与实验测量数据及MCNP程序计算结果进行比较,发现中子泄漏谱的符合程度较好,而光子泄漏谱检验中发现大多数核素都出现了不同程度的高估。通过对GENDF格式到AMPX格式的转换程序MILER-4进行修正,解决了这一问题。通过对多群常数库的屏蔽基准验证,进一步证明了该库的可靠性。OKTAVIAN pulsed sphere experiment was used for Shielding Benchmarks of the AMPX formatted multi-group (238n-48γ) coupled neutron-gamma cross-section library for Thorium Molten Salt Reactor, of which the following isotopes/elements were checked-F, Li, Be, C, Al, Si, Cr, Ni, Zr, Co, Cu, Mn, Mo, Nb, Ti, W. One dimension shielding problem was calculated using XSDRN-PM program of SCALE 5.1 code system and results were compared with experiment results and MCNP calculated results, which shows that neutron leakage spectra agree well. Calculated results of photon leakage spectra of most facilities compared with MCNP results and experiment data are over-rated. MILER-4 code which is used for converting GENDF files produced by NJOY to the AMPX master library format is revised to solve this problem. The shielding benchmark verifications confirm the reliability of this new library.     

Recent Advances for the Quadratic Assignment Problem with Special Emphasis on Instances that are Difficult for Meta-Heuristic Methods

This paper reports heuristic and exact solution advances for the Quadratic Assignment Problem (QAP).QAPinstances most often discussed in the literature are relatively well solved by heuristic approaches. Indeed, solutions at a fraction of one percent from the best known solution values are rapidly found by most heuristic methods. Exact methods are not able to prove optimality for these instances as soon as the problem size approaches 30 to 40. This article presents new QAP instances that are ill conditioned for many metaheuristic-based methods. However, these new instances are shown to be solved relatively well by some exact methods, since problem instances up to a size of 75 have been exactly solved.     

Performance of SOPPA-based methods in the calculation of vertical excitation energies and oscillator strengths

We present two new modifications of the second-order polarization propagator approximation (SOPPA), SOPPA(SCS-MP2) and SOPPA(SOS-MP2), which employ either spin-component-scaled or scaled opposite-spin MP2 correlation coefficients instead of the regular MP2 coefficients. The performance of these two methods, the original SOPPA method as well as SOPPA(CCSD) and RPA(D) in the calculation of vertical electronic excitation energies and oscillator strengths is investigated for a large benchmark set of 28 medium-sized molecules with 139 singlet and 71 triplet excited states. The results are compared with the corresponding CC3 and CASPT2 results from the literature for both the TZVP set and the larger and more diffuse aug-cc-pVTZ basis set. In addition, the results with the aug-cc-pVTZ basis set are compared with the theoretical best estimates for this benchmark set. We find that the original SOPPA method gives overall the smallest mean deviations from the reference values and the most consistent results.