Synthesis of P,N-2,2′-biphenyl derivatives with central chirality

Enantiopure 2-(dicyclohexylphosphino)-1,1′-biphenyl derivatives substituted in the 2′-position by a chiral amino group were prepared. For the compound bearing an acyclic chiral chain, the key step was a Suzuki coupling between bromobenzeneboronic acid and N-Boc-iodoaniline whereas an aromatic nucleophilic substitution allowed the introduction of a chiral pyrrolidine in the 2′-position of the biphenyl backbone. The efficiency of the P,N-biphenyl pyrrolidine derivatives as ligands in Pd-catalyzed arylaminations compares well with that of DavePhos ligand.     

On the singular set of the parabolic obstacle problem

This paper is devoted to regularity results and geometric properties of the singular set of the parabolic obstacle problem with variable right-hand side. Making use of a monotonicity formula for singular points, we prove the uniqueness of blow-up limits at singular points. These results apply to parabolic obstacle problem with variable coefficients.     

Gravitational radiation from inspiralling compact binaries completed at the third post-Newtonian order

The gravitational radiation from point particle binaries is computed at the third post-Newtonian (3PN) approximation of general relativity. Three previously introduced ambiguity parameters, coming from the Hadamard self-field regularization of the 3PN source-type mass quadrupole moment, are consistently determined by means of dimensional regularization, and proved to have the values xi=-9871/9240, kappa=0, and zeta=-7/33. These results complete the derivation of the general relativistic prediction for compact binary inspiral up to 3.5PN order, and should be of use for searching and deciphering the signals in the current network of gravitational wave detectors.     

Nonadiabatic Multielectron Dynamics in Strong Field Molecular Ionization

We report the observation of a general strong field ionization mechanism due to highly nonadiabatic multielectron excitation dynamics in polyatomic molecules. We observe that such excitation mechanisms greatly affect molecular ionization, fragmentation, and energetics. We characterized this phenomenon as a function of optical frequency, intensity, and molecular properties.     

Effects of thermo-hygro-mechanical densification on the surface characteristics of trembling aspen and hybrid poplar wood veneers

The effect of thermo-hygro-mechanical (THM) densification temperature on the surface color, roughness, wettability, and chemical composition of trembling aspen (Populus tremuloides) and hybrid poplar (Populus maximowiczii × P. balsamifera) veneers was investigated. Veneers were subjected to four THM densification temperatures (160 °C, 180 °C, 200 °C, and 220 °C). Veneer color darkened with increasing THM densification temperature. Surface roughness decreased between 160 °C and 200 °C. Wettability decreased after THM densification, but no significant difference was found between treated specimens. ATR-FTIR and XPS results confirmed that THM densification caused major chemical changes in veneer surfaces, and more pronounced at temperatures higher than 160 °C.     

Multivariate curve resolution: A review of advanced and tailored applications and challenges

Multivariate curve resolution (MCR) is a widespread methodology for the analysis of process data in many different application fields. This article intends to propose a critical review of the recently published works. Particular attention will be paid to situations requiring advanced and tailored applications of multivariate curve resolution, dealing with improvements in preprocessing methods, multi-set data arrangements, tailored constraints, issues related to non-ideal noise structure and deviation to linearity. These analytical issues are tackling the limits of applicability of MCR methods and, therefore, they can be considered as the most challenging ones.     

The benzophenone S1(n,pi*) --> T1(n,pi*) states intersystem crossing reinvestigated by ultrafast absorption spectroscopy and multivariate curve resolution

The well-known benzophenone intersystem crossing from S(1)(n,pi*) to T(1)(n,pi*) states, for which direct transition is forbidden by El-Sayed rules, is reinvestigated by subpicosecond time-resolved absorption spectroscopy and effective data analysis for various excitation wavelengths and solvents. Multivariate curve resolution alternating least-squares analysis is used to perform bilinear decomposition of the time-resolved spectra into pure spectra of overlapping transient species and their associated time-dependent concentrations. The results suggest the implication of an intermediate (IS) in the relaxation process of the S(1) state. Therefore, a two step kinetic model, S(1) --> IS --> T(1), is successfully implemented as an additional constraint in the soft-modeling algorithm. Although this intermediate, which has a spectrum similar to the one of T(1)(n,pi*) state, could be artificially induced by vibrational relaxation, it is tentatively assigned to a hot T(1)(n,pi*) triplet state. Two characteristic times are reported for the transition S(1) --> IS and IS --> T(1), approximately 6.5 ps and approximately 10 ps respectively, without any influence of the solvent. Moreover, an excitation wavelength effect is discovered suggesting the participation of unrelaxed singlet states in the overall process. To go further discussing the spectroscopic relevancy of IS and to rationalize the expected involvement of the T(2)(pi,pi*) state, we also investigate 4-methoxybenzophenone. For this neighboring molecule, triplet energy level is tunable through solvent polarity and a clear correlation is established between the intermediate resolved by multivariate data analysis and the presence of a T(2)(pi,pi*) above the T(1)(n,pi*) triplet. It is therefore proposed that the benzophenone intermediate species is a T(1)(n,pi*) high vibrational level in interaction with T(2)(pi,pi*) state.     

Efficient simulation of tail probabilities of sums of correlated lognormals

We consider the problem of efficient estimation of tail probabilities of sums of correlated lognormals via simulation. This problem is motivated by the tail analysis of portfolios of assets driven by correlated Black-Scholes models. We propose two estimators that can be rigorously shown to be efficient as the tail probability of interest decreases to zero. The first estimator, based on importance sampling, involves a scaling of the whole covariance matrix and can be shown to be asymptotically optimal. A further study, based on the Cross-Entropy algorithm, is also performed in order to adaptively optimize the scaling parameter of the covariance. The second estimator decomposes the probability of interest in two contributions and takes advantage of the fact that large deviations for a sum of correlated lognormals are (asymptotically) caused by the largest increment. Importance sampling is then applied to each of these contributions to obtain a combined estimator with asymptotically vanishing relative error.     

Efficient simulation and conditional functional limit theorems for ruinous heavy-tailed random walks

The contribution of this paper is to introduce change of measure based techniques for the rare-event analysis of heavy-tailed random walks. Our changes of measures are parameterized by a family of distributions admitting a mixture form. We exploit our methodology to achieve two types of results. First, we construct Monte Carlo estimators that are strongly efficient (i.e. have bounded relative mean squared error as the event of interest becomes rare). These estimators are used to estimate both rare-event probabilities of interest and associated conditional expectations. We emphasize that our techniques allow us to control the expected termination time of the Monte Carlo algorithm even if the conditional expected stopping time (under the original distribution) given the event of interest is infinity–a situation that sometimes occurs in heavy-tailed settings. Second, the mixture family serves as a good Markovian approximation (in total variation) of the conditional distribution of the whole process given the rare event of interest. The convenient form of the mixture family allows us to obtain functional conditional central limit theorems that extend classical results in the literature.