Effect of the Terminal Acceptor Unit on the Performance of Non-Fullerene Indacenodithiophene Acceptors in Organic Solar Cells

Four acceptor–donor–acceptor (A–D–A)-type molecules bearing indacenodithiophene as donating central core and various end-capping acceptor units have been designed and synthesised as n-type materials suitable for organic solar cells (OSCs). The studied optical and electrochemical properties supported by theoretical calculations revealed that the nature and the strength of the terminal groups exert a decisive influence on the polymer bulk-heterojunction OSC performance.     

Automatic compatibility tests of HSQC NMR spectra with proposed structures of chemical compounds

A recently introduced similarity measure is extended here for comparing two-dimensional spectra. Its applicability is demonstrated with heteronuclear single-quantum correlation (HSQC) NMR spectra. For testing the compatibility of a spectrum with the proposed chemical structure, first, the spectrum is predicted on the basis of that structure and then, the proposed comparison algorithm is applied. In this context, the topics of optimization are peak picking, signal intensity measures, and optimizing the parameters of the two-dimensional comparison method. The performance is analyzed with a test set of 289 structures of organic compounds and their HSQC and ¹H NMR spectra. The results obtained with HSQC spectra are better than those achieved using the previously described one-dimensional similarity test with ¹H NMR spectra alone.     

Polynomial time approximation schemes for general multiprocessor job shop scheduling

We study preemptive and non-preemptive versions of the general multiprocessor job shop scheduling problem: Given a set of n tasks each consisting of at most μ ordered operations that can be processed on different (possibly all) subsets of m machines with different processing times, compute a schedule (preemptive or non-preemptive, depending on the model) with minimum makespan where operations belonging to the same task have to be scheduled according to the specified order. We propose algorithms for both preemptive and non-preemptive variants of this problem that compute approximate solutions of any positive ε accuracy and run in O(n) time for any fixed values of m, μ, and ε. These results include (as special cases) many recent developments on polynomial time approximation schemes for scheduling jobs on unrelated machines, multiprocessor tasks, and classical open, flow and job shops.     

On the Complexity of Semidefinite Programs

We show that the feasibility of a system of m linear inequalities over the cone of symmetric positive semidefinite matrices of order n can be tested in mn arithmetic operations with -bit numbers, where l is the maximum binary size of the input coefficients. We also show that any feasible system of dimension (m,n) has a solution X such that log||X|| .     

Density functional theory investigation of competitive free-radical processes during the thermal cracking of methylated polyaromatics: estimation of kinetic parameters

Density functional B3LYP and BH&HLYP calculations with the 6-31G** basis set have been performed to investigate elementary reactions playing an important role in the pyrolysis of 1-methylnaphthalene. The pathways describing the destiny of the main radicals, H, methyl, hydromethylnaphthyl and methylnaphthyl, have been studied. At low temperature, addition of H atoms on the aromatic ring is favored over hydrogen abstraction. Except at low temperature (below 400 K), the hydromethylnaphthyl radical undergoes preferentially a loss of hydrogen rather than a bimolecular hydrogen transfer with methylnaphthalene or addition reaction on methylnaphthalene forming a hydrogenated dimer. In the range 400-750 K, the formation of methane by hydrogen abstraction of methyl radical on methylnaphthalene is predominant compared to the formation of hydrodimethylnaphthalenes by addition reaction. Rate constants of reactions describing the formation of heavy products like methyldinaphthylmethanes or dimethylbinaphthalenes have been calculated and discussed. They are also compared to recombination reactions from the literature. Rate constants of these reactions have been computed using transition state theory and can be integrated in kinetic radical schemes of methylated polyaromatic compounds pyrolysis from geological to laboratory conditions.     

Calculating potentials of mean force and diffusion coefficients from nonequilibrium processes without Jarzynski's equality

In general, the direct application of the Jarzynski equality (JE) to reconstruct potentials of mean force (PMFs) from a small number of nonequilibrium unidirectional steered molecular-dynamics (SMD) paths is hindered by the lack of sampling of extremely rare paths with negative dissipative work. Such trajectories that transiently violate the second law of thermodynamics are crucial for the validity of JE. As a solution to this daunting problem, we propose a simple and efficient method, referred to as the FR method, for calculating simultaneously both the PMF U(z) and the corresponding diffusion coefficient D(z) along a reaction coordinate z for a classical many-particle system by employing a small number of fast SMD pullings in both forward (F) and time reverse (R) directions, without invoking JE. By employing Crooks [Phys. Rev. E 61, 2361 (2000)] transient fluctuation theorem (that is more general than JE) and the stiff-spring approximation, we show that (i) the mean dissipative work W(d) in the F and R pullings is the same, (ii) both U(z) and W(d) can be expressed in terms of the easily calculable mean work of the F and R processes, and (iii) D(z) can be expressed in terms of the slope of W(d). To test its viability, the FR method is applied to determine U(z) and D(z) of single-file water molecules in single-walled carbon nanotubes (SWNTs). The obtained U(z) is found to be in very good agreement with the results from other PMF calculation methods, e.g., umbrella sampling. Finally, U(z) and D(z) are used as input in a stochastic model, based on the Fokker-Planck equation, for describing water transport through SWNTs on a mesoscopic time scale that in general is inaccessible to MD simulations.     

Computing optimal preemptive schedules for parallel tasks: linear programming approaches

 We study the problem of scheduling a set of n independent parallel tasks on m processors, where in addition to the processing time there is a size associated with each task indicating that the task can be processed on any subset of processors of the given size. Based on a linear programming formulation, we propose an algorithm for computing a preemptive schedule with minimum makespan, and show that the running time of the algorithm depends polynomially on m and only linearly on n. Thus for any fixed m, an optimal preemptive schedule can be computed in O(n) time. We also present extensions of this approach to other (more general) scheduling problems with malleable tasks, due dates and maximum lateness minimization. Received: November 1999 / Accepted: November 2002 Publication online: December 19, 2002 RID="⋆" ID="⋆" This work was done while the authors were associated with the research institutes IDSIA Lugano and MPII Saarbrücken and were supported in part by the Swiss Office Fédéral de l'éducation et de la Science project n 97.0315 titled ``Platform' and by EU ESPRIT LTR Project No. 20244 (ALCOM-IT)     

Theoretical prediction of spectral and optical properties of bacteriochlorophylls in thermally disordered LH2 antenna complexes

A general approach for calculating spectral and optical properties of pigment-protein complexes of known atomic structure is presented. The method, that combines molecular dynamics simulations, quantum chemistry calculations, and statistical mechanical modeling, is demonstrated by calculating the absorption and circular dichroism spectra of the B800-B850 bacteriochlorophylls of the LH2 antenna complex from Rs. molischianum at room temperature. The calculated spectra are found to be in good agreement with the available experimental results. The calculations reveal that the broadening of the B800 band is mainly caused by the interactions with the polar protein environment, while the broadening of the B850 band is due to the excitonic interactions. Since it contains no fitting parameters, in principle, the proposed method can be used to predict optical spectra of arbitrary pigment-protein complexes of known structure.