ALBERT

Description: Quantum-chemical computations of nuclear quadrupole-coupling parameters for 24 open-shell states of small molecules based on non-relativistic and spin-free exact two-component (SFX2C) relativistic equation-of-motion coupled-cluster (EOM-CC) as well as spin-orbital-based restricted open-shell Hartree-Fock coupled-cluster (ROHF-CC) methods are reported. Relativistic effects, the performance of the EOM-CC and ROHF-CC methods for treating electron correlation, as well as basis-set convergence have been carefully analyzed. Consideration of relativistic effects is necessary for accurate calculations on systems containing third-row (K-Kr) and heavier elements, as expected, and the SFX2C approach is shown to be a useful cost-effective option here. Further, it is demonstrated that the EOM-CC methods constitute flexible and accurate alternatives to the ROHF-CC methods in the calculations of nuclear quadrupole-coupling parameters for open-shell states.

Description: A systematic relativistic coupled-cluster study is reported on the harmonic vibrational frequencies of the O h , C 3v , and C 2v conformers of XeF 6 , with scalar-relativistic effects efficiently treated using the spin-free exact two-component theory in its one-electron variant (SFX2C-1e). Atomic natural orbital type basis sets recontracted for the SFX2C-1e scheme have been shown to provide rapid basis-set convergence for the vibrational frequencies. SFX2C-1e as well as complementary pseudopotential based computations consistently predicts that both O h and C 3v structures are local minima on the potential energy surface, while the C 2v structure is a transition state. Qualitative disagreement between the present results for the O h structure and those from CCSD(T)-F12b calculations [Peterson et al. , J. Phys. Chem. A 116 , 9777 (2012)], which yielded a triply degenerate imaginary frequency for the O h structure, is attributed here to the high sensitivity of the computed harmonic frequencies of the t 1u bending modes to the basis-set effects of triples contributions.

Description: A new design of conjugated heat transfer in double-pass parallel-plate laminar countercurrent operations of power law fluids under wall isoflux was investigated experimentally and theoretically. The analytical solutions were obtained with a superposition model by introducing an eigenfunction expansion in terms of a power series for the homogeneous part and an asymptotic solution for the inhomogeneous part. The influence of the power law index on the average Nusselt numbers with the various design and operating parameters is also delineated. The theoretical predictions of the experimental results are represented graphically. The heat transfer performance was considerably improved when compared with a single-pass parallel-plate heat exchanger (without inserting a solid separator sheet). Suitable adjustments of the solid separator sheet position can effectively enhance the heat transfer efficiencies for such a recycling double-pass device, as compared with the efficiencies of single- and double-pass devices.

Description: In this study, eight types of materials including nanoparticles (Cu and CaCO3), metallic ions (Ca2+ and Cu2+), and amino acid substances (serine, tyrosine, sericin amino acid, and fibroin amino acid) were used as additives in silkworm diets to obtain in-situ modified silk fiber composites. The results indicate that tyrosine and fibroin amino acids significantly increase potassium content in silk fibers and induce the transformation of α-helices and random coils to β-sheet structures, resulting in higher crystallinities and better mechanical properties. However, the other additives-modified silk fibers show a decrease in β-sheet contents and a slight increase or even decrease in tensile strengths. This finding provides a green and effective approach to produce mechanically enhanced silk fibers with high crystallinity on a large scale. Moreover, the modification mechanisms of these additives were discussed in this study, which could offer new insights into the design and regulation of modified fibers or composites with desirable properties and functions.

Description: This paper presents a novel stochastic predictive tracking control strategy for nonlinear and non-Gaussian stochastic systems based on the single neuron controller structure in the framework of information theory. Firstly, in order to characterize the randomness of the control system, survival information potential (SIP), instead of entropy, is adopted to formulate the performance index, which is not shift-invariant, i.e., its value varies with the change of the distribution location. Then, the optimal weights of the single neuron controller can be obtained by minimizing the presented SIP based predictive control criterion. Furthermore, mean-square convergence of the proposed control algorithm is also analyzed from the energy conservation perspective. Finally, a numerical example is given to show the effectiveness of the proposed method.

Description: Photoionization cross sections and partial ion yields of Xe and XeF 2 from Xe 3d 5/2 , Xe 3d 3/2 , and F 1s subshells in the 660–740 eV range are compared to explore effects of the F ligands. The Xe 3d- ϵ f continuum shape resonances dominate the photoionization cross sections of both the atom and molecule, but prominent resonances appear in the XeF 2 cross section due to nominal excitation of Xe 3d and F 1s electrons to the lowest unoccupied molecular orbital (LUMO), a delocalized anti-bonding MO. Comparisons of the ion products from the atom and molecule following Xe 3d photoionization show that the charge-state distribution of Xe ions is shifted to lower charge states in the molecule along with production of energetic F + and F 2+ ions. This suggests that, in decay of a Xe 3d core hole, charge is redistributed to the F ligands and the system dissociates due to Coulomb repulsion. The ion products from excitation of the F 1s-LUMO resonance are different and show strong increases in the yields of Xe + and F + ions. The subshell ionization thresholds, the LUMO resonance energies, and their oscillator strengths are calculated by relativistic coupled-cluster methods and agree well with measurements.

Description: For some groups of organisms, DNA barcoding can provide a useful tool in taxonomy, evolutionary biology, and biodiversity assessment. However, the efficacy of DNA barcoding depends on the degree of sampling per species, because a large enough sample size is needed to provide a reliable estimate of genetic polymorphism and for delimiting species. We used a simulation approach to examine the effects of sample size on four estimators of genetic polymorphism related to DNA barcoding: mismatch distribution, nucleotide diversity, the number of haplotypes, and maximum pairwise distance. Our results showed that mismatch distributions derived from subsamples of ≥20 individuals usually bore a close resemblance to that of the full dataset. Estimates of nucleotide diversity from subsamples of ≥20 individuals tended to be bell-shaped around that of the full dataset, whereas estimates from smaller subsamples were not. As expected, greater sampling generally led to an increase in the number of haplotypes. We also found that subsamples of ≥20 individuals allowed a good estimate of the maximum pairwise distance of the full dataset, while smaller ones were associated with a high probability of underestimation. Overall, our study confirms the expectation that larger samples are beneficial for the efficacy of DNA barcoding and suggests that a minimum sample size of 20 individuals is needed in practice for each population. A simulation study was done to examine the effects of sample size on DNA barcoding via four estimators of genetic polymorphism: mismatch distribution, nucleotide diversity, the number of haplotypes, and maximum pairwise distance. While supporting the expectation that larger samples are beneficial for the efficacy of DNA barcoding with more evidence, a minimum sample size of 20 individuals is suggested in practice for each population.

Description: Increasing the combustion efficiency of power plant boilers and reducing pollutant emissions are important for energy conservation and environmental protection. The power plant boiler combustion process is a complex multi-input/multi-output system, with a high degree of nonlinearity and strong coupling characteristics. It is necessary to optimize the boiler combustion model by means of artificial intelligence methods. However, the traditional intelligent algorithms cannot deal effectively with the massive and high dimensional power station data. In this paper, a distributed combustion optimization method for boilers is proposed. The MapReduce programming framework is used to parallelize the proposed algorithm model and improve its ability to deal with big data. An improved distributed extreme learning machine is used to establish the combustion system model aiming at boiler combustion efficiency and NOx emission. The distributed particle swarm optimization algorithm based on MapReduce is used to optimize the input parameters of boiler combustion model, and weighted coefficient method is used to solve the multi-objective optimization problem (boiler combustion efficiency and NOx emissions). According to the experimental analysis, the results show that the method can optimize the boiler combustion efficiency and NOx emissions by combining different weight coefficients as needed.

Description: This work deals with the perturbative treatment of spin-orbit-coupling (SOC) effects within the spin-free exact two-component theory in its one-electron variant (SFX2C-1e). We investigate two schemes for constructing the SFX2C-1e SOC matrix: the SFX2C-1e+SOC [der] scheme defines the SOC matrix elements based on SFX2C-1e analytic-derivative theory, hereby treating the SOC integrals as the perturbation; the SFX2C-1e+SOC [fd] scheme takes the difference between the X2C-1e and SFX2C-1e Hamiltonian matrices as the SOC perturbation. Furthermore, a mean-field approach in the SFX2C-1e framework is formulated and implemented to efficiently include two-electron SOC effects. Systematic approximations to the two-electron SOC integrals are also proposed and carefully assessed. Based on benchmark calculations of the second-order SOC corrections to the energies and electrical properties for a set of diatomic molecules, we show that the SFX2C-1e+SOC [der] scheme performs very well in the computation of perturbative SOC corrections and that the “2eSL” scheme, which neglects the (SS|SS)-type two-electron SOC integrals, is both efficient and accurate. In contrast, the SFX2C-1e+SOC [fd] scheme turns out to be incompatible with a perturbative treatment of SOC effects. Finally, as a first chemical application, we report high-accuracy calculations of the 201 Hg quadrupole-coupling parameters of the recently characterized ethylmercury hydride (HHgCH 2 CH 3 ) molecule based on SFX2C-1e coupled-cluster calculations augmented with second-order SOC corrections obtained at the Hartree-Fock level using the SFX2C-1e+SOC [der]/2eSL scheme.