Chemical Bonding in [Fe(η4-P4)2]2- and Related Complexes.

Quantum chemical calculations of the six valence isoelectronic complexes [FeL2]2-, [CoL2]-, and NiL2 with L = η4-P4, η4-C4H4 using density functional theory have been carried out. The molecular structures were investigated with a variety of methods. The analysis of the electronic structure in [Fe(η4-P4)2]2- shows that the bonding situation is very similar to valence isoelectronic Ni(η4-C4H4)2. The orbital interactions in the 18 electron complexes [TML2]q (TMq = Fe2-, Co-, Ni) come mainly from TM(dπ)→L2 backdonation, enhanced by smaller contributions from TM(dδ)→L2 backdonation and TM(s)←L2 donation. Calculations of the six TML2 species indicate that all of them are viable candidates for synthetic work. The bonding situation is very similar and can straightforwardly be explained with the Dewar-Chatt-Duncanson bonding model in terms of dative bonding between d10 metal atoms and the ligands in the electronic singlet state. EDA-NOCV calculations using the ligands and the metal atoms with different charges and electronic states indicate that the metal-ligand bonds in the charged complexes [FeL2]2- and [CoL2]- are best described with fragments in the electronic triplet state between the metal atoms with d8 configuration and triplet ligands. The singlet fragments give the degenerate TM(dπ)→L2 π backdonation as the strongest component, whereas the triplet fragments have the related electron-sharing TMq (dπ)-(L2)2- π bonding as the major component, differing only by the assignment of the bonded two electrons to one or both fragments. The calculations of the charge distribution using the Hirshfeld and Voronoi partitioning methods suggest that the metal atoms are nearly neutral or carry small negative charges in all complexes. The NBO method gives erratic charges, because of the neglect of the 4p AOs of the transition metals as genuine valence orbitals.

Stabilization of Cyclic C4 by Four Donor Ligands: A Theoretical Study of (L)4C4 (L = Carbene).

Quantum chemical studies using density functional theory were carried out for the (L)4C4 complexes with L = cAAC, DAC, NHC, SNHC, MIC1, and MIC2. The results show that the title complexes are highly stable with respect to dissociation, (L)4C4 → C4 + 4L. However, their stability with respect to (L)4C4 → 2(L)2C2 is crucial for the assessment of their experimental viability. The (L)4C4 complexes with L = cAAC and DAC dissociate exergonically at room temperature into two (L)2C2 units. In contrast, the other (L)4C4 complexes with L = NHC, SNHC, MIC1, and MIC2 are thermochemically stable with respect to dissociation, (L)4C4 → 2(L)2C2. The computed adiabatic ionization potentials of (L)4C4 complexes with L = NHC, MIC1, and MIC2 are lower than those for the cesium atom. Particularly, (MIC1)4C4 and (MIC2)4C4 will very easily lose electrons to form cationic complexes. The SNHC ligand is the best for the experimental realization of (L)4C4 complexes, followed by NHC. The bonding analysis using charge and energy decomposition methods suggests that the (L)3C4-CL bond can be best described as a typical electron-sharing double bond with a strong σ-bond and a weaker π-bond. Therefore, the core bonding pictures in the title complexes resemble a [4]radialene. Larger substituents at the carbene ligands enhance the stability of the complexes (L)4C4 against dissociation.

Conformal Boundary Conditions of Symmetry-Enriched Quantum Critical Spin Chains.

Some quantum critical states cannot be smoothly deformed into each other without either crossing some multicritical points or explicitly breaking certain symmetries even if they belong to the same universality class. This brings up the notion of "symmetry-enriched" quantum criticality. While recent works in the literature focused on critical states with robust degenerate edge modes, we propose that the conformal boundary condition (B.C.) is a more generic characteristic of such quantum critical states. We show that in two families of quantum spin chains, which generalize the Ising and the three-state Potts models, the quantum critical point between a symmetry-protected topological phase and a symmetry-breaking order realizes a conformal B.C. distinct from the simple Ising and Potts chains. Furthermore, we argue that the conformal B.C. can be derived from the bulk effective field theory, which realizes a novel bulk-boundary correspondence in symmetry-enriched quantum critical states.

How to capture C2O2: structures and bonding of neutral and charged complexes [(NHC)-C2O2-(NHC)]q (NHC = N-heterocyclic carbene; q = 0, 1+, 2+).

We present the results of DFT calculations and a thorough bonding analysis of the neutral and charged complexes of the elusive C2O2 species stabilized by two NHC ligands. It is shown that the thermodynamic stability of the neutral complex [(NHC)-C2O2-(NHC)] is due to the low-lying triplet state of [NHC-CO] (T), which is only 3.2 kcal mol-1 higher in energy than the singlet state [NHC-CO] (S), while the triplet state of CO is 131.9 kcal mol-1 above the singlet. The much lower S/T gap of [NHC-CO] than in CO comes from the charge donation of NHC into the degenerate π* LUMO of CO and the concomitant mixing of the LUMO of NHC with the degenerate π* LUMO of CO, which strongly lowers the energy difference between HOMO and LUMO in the complex. The energy gain resulting from the formation of the CC double bond compensates the singlet-triplet gap and the thermodynamic instability of the fragments [NHC-CO] (S). The dissociation of neutral [(NHC)-C2O2-(NHC)] to 2NHC and 2CO molecules is calculated to be endothermic by Do = 78.2 kcal mol-1. The bonding analysis indicates that the neutral and the charged molecules [(NHC)-C2O2-(NHC)]q have a central unit with C-C single bonds, where a combination of electron sharing and s dative interactions leads to very strong carbon-carbon bonds complemented by minor π-donation, which make all systems stable with respect to dissociation reactions. The central C2O2 fragment carries a large negative partial charge in the neutral and singly charged compounds [(NHC)-C2O2-(NHC)]0,1+, while it is neutral in the dication [(NHC)-C2O2-(NHC)]2+.

Covalent Bonding Between Be+ and CO2 in BeOCO+ with a Surprisingly High Antisymmetric OCO Stretching Vibration.

The cationic complex BeOCO+ is produced in a solid neon matrix. Infrared absorption spectroscopic study shows that it has a very high antisymmetric OCO stretching vibration of 2418.9 cm-1, which is about 71 cm-1 blue-shifted from that of free CO2. The quantum chemical calculations are in very good agreement with the experimental observation. Depending on the theoretical method, a linear or quasi-linear structure is predicted for the cation. The analysis of the electronic structure shows that the bonding of Be+ to one oxygen atom induces very little charge migration between the two moieties, but it causes a significant change in the σ-charge distribution that strengthens the terminal C-O bond, leading to the observed blue shift. The bonding analysis reveals that the Be+ ← OCO donation results in strong binding due to the interference of the wave function and a charge polarization within the CO2 fragment and hybridization to Be+ but only negligible charge donation.

Computational Mechanistic Study of Brønsted Acid-Catalyzed Unsymmetrical 1,2,4,5-Tetrazines Synthesis.

Density functional theory (DFT) calculations were conducted to gain insight into the reaction mechanism of the Brønsted acid-catalyzed unsymmetrical 1,2,4,5-tetrazine synthesis. Various possible reaction pathways were considered, and the most favorable one can be characterized via sequential six steps, including addition of DCM to hydrazine 1 giving complex IM4, N-H bond activation in IM4 mediated by sulfur, AcOH-assisted substitution of 3 with sulfur-activated hydrazine 2, HNO2-assisted addition of nitrile to intermediate 8, cyclization, and intramolecular elimination leading to the final product 7. Among the six steps, sulfur activation of IM4 N-H bond is found to be the rate-determining step (RDS). The mechanism rationalizes the experimental observation that 2 equiv of sulfur leads to the best yield of product. Furthermore, we disclosed that the Brønsted acid additives (i.e., acetic acid and nitrous acid) served triple roles as catalyst, proton shuttle, and hydrogen bond donor and acceptor in the whole catalysis.

Engineering Surface Critical Behavior of (2+1)-Dimensional O(3) Quantum Critical Points.

Surface critical behavior (SCB) refers to the singularities of physical quantities on the surface at the bulk phase transition. It is closely related to and even richer than the bulk critical behavior. In this work, we show that three types of SCB universality are realized in the dimerized Heisenberg models at the (2+1)-dimensional O(3) quantum critical points by engineering the surface configurations. The ordinary transition happens if the surface is gapped in the bulk disordered phase, while the gapless surface state generally leads to the multicritical special transition, even though the latter is precluded in classical phase transitions because the surface is in the lower critical dimension. An extraordinary transition is induced by the ferrimagnetic order on the surface of the staggered Heisenberg model, in which the surface critical exponents violate the results of the scaling theory and thus seriously challenge our current understanding of extraordinary transitions.

Identification and Analysis of Genes Related to Testicular Size in 14-Day-Old Piglets.

The RNA-Seq technology was used to screen the key genes that affect the early development of the testes of Duroc × Landrace × Yorkshire piglets, to determine the regulatory pathway and provide reference for subsequent reproductive performance research, breeding, and other production practices. This study selected 14-day-old Duroc × Landrace × Yorkshire piglets as the trial animals. Testes from piglets with similar weights and no pathological changes were divided into small testis (ST) and large testis (LT) groups, and the RNA-Seq screening of differentially expressed genes (DEGs) was performed to find candidate genes and regulatory pathways related to early testicular development. The results show that 570 DEGs were found in the ST and LT groups, with 281 upregulated and 289 downregulated. The DEGs were mainly enriched on 47 gene ontology (GO) functional items. The Kyoto encyclopedia of genes and genotypes (KEGG) enrichment analysis found that there were 44 significantly enriched KEGG signal pathways, and the regulation of testicular development mainly focused on the arachidonic acid metabolism, Wnt signaling pathway and GnRH secretion pathways. The PTGES, SFRP1, SPP1, PLA2G4E, KCNJ5, PTGS2, and HCN1 genes were found to be as closely related to the testicular development of these Duroc × Landrace × Yorkshire piglets, and the differential gene expression was consistent with the real-time quantitative reverse transcription PCR (real-time qRT-PCR) validation results. This study was validated by high-throughput sequencing analysis and real-time qRT-PCR, and showed that the PTGES, SFRP1, SPP1, PLA2G4E, KCNJ5, PTGS2, and HCN1 genes may be involved in the regulation of germ cell development, spermatogenesis and semen traits. These should be further studied as candidate genes for early testicular development and reproductive trait regulation in boars.

Quantum criticality of a Z_{3}-symmetric spin chain with long-range interactions.

Based on large-scale density matrix renormalization group techniques, we investigate the critical behaviors of quantum three-state Potts chains with long-range interactions. Using fidelity susceptibility as an indicator, we obtain a complete phase diagram of the system. The results show that as the long-range interaction power α increases, the critical points f_{c}^{*} shift towards lower values. In addition, the critical threshold α_{c}(≈1.43) of the long-range interaction power is obtained for the first time by a nonperturbative numerical method. This indicates that the critical behavior of the system can be naturally divided into two distinct universality classes, namely the long-range (α<α_{c}) and short-range (α>α_{c}) universality classes, qualitatively consistent with the classical ϕ^{3} effective field theory. This work provides a useful reference for further research on phase transitions in quantum spin chains with long-range interaction.

Biotic interactions contribute more than environmental factors and geographic distance to biogeographic patterns of soil prokaryotic and fungal communities.

Recent studies have shown distinct soil microbial assembly patterns across taxonomic types, habitat types and regions, but little is known about which factors play a dominant role in soil microbial communities. To bridge this gap, we compared the differences in microbial diversity and community composition across two taxonomic types (prokaryotes and fungi), two habitat types (Artemisia and Poaceae) and three geographic regions in the arid ecosystem of northwest China. To determine the main driving factors shaping the prokaryotic and fungal community assembly, we carried out diverse analyses including null model, partial mantel test and variance partitioning analysis etc. The findings suggested that the processes of community assembly were more diverse among taxonomic categories in comparison to habitats or geographical regions. The predominant driving factor of soil microbial community assembly in arid ecosystem was biotic interactions between microorganisms, followed by environmental filtering and dispersal limitation. Network vertex, positive cohesion and negative cohesion showed the most significant correlations with prokaryotic and fungal diversity and community dissimilarity. Salinity was the major environmental variable structuring the prokaryotic community. Although prokaryotic and fungal communities were jointly regulated by the three factors, the effects of biotic interactions and environmental variables (both are deterministic processes) on the community structure of prokaryotes were stronger than that of fungi. The null model revealed that prokaryotic community assembly was more deterministic, whereas fungal community assembly was structured by stochastic processes. Taken together, these findings unravel the predominant drivers governing microbial community assembly across taxonomic types, habitat types and geographic regions and highlight the impacts of biotic interactions on disentangling soil microbial assembly mechanisms.

Solar park promoted microbial nitrogen and phosphorus cycle potentials but reduced soil prokaryotic diversity and network stability in alpine desert ecosystem.

Solar park (SP) is rapidly growing throughout the planet due to the increasing demand for low-carbon energy, which represents a remarkable global land-use change with implications for the hosting ecosystems. Despite dozens of studies estimating the environmental impacts of SP based on local microclimate and vegetation, responses of soil microbial interactions and nutrient cycle potentials remain poorly understood. To bridge this gap, we investigated the diversity, community structure, complexity, and stability of co-occurrence network and soil enzyme activities of soil prokaryotes and fungi in habitats of ambient, the first, and sixth year since solar park establishment. Results revealed different response patterns of prokaryotes and fungi. SP led to significant differences in both prokaryotic and fungal community structures but only reduced prokaryotic alpha diversity significantly. Co-occurrence network analysis revealed a unimodal pattern of prokaryotic network features and more resistance of fungal networks to environmental variations. Microbial nitrogen and phosphorus cycle potentials were higher in SP and their variances were more explained by network features than by diversity and environmental characteristics. Our findings revealed for the first time the significant impacts of SP on soil prokaryotic and fungal stability and functional potentials, which provides a microbial insight for impact evaluation and evidence for the optimization of solar park management to maximize the delivery of ecosystem services from this growing land use.

Phase transitions in a three-dimensional Ising model with cluster weight studied by Monte Carlo simulations.

The loop model is an important model of statistical mechanics and has been extensively studied in two-dimensional lattices. However, it is still difficult to simulate the loop model directly in three-dimensional lattices, especially in lattices with coordination numbers larger than 3. In this paper, a cluster weight Ising model is proposed by introducing an additional cluster weight n in the partition function of the traditional Ising model. This model is equivalent to the loop model on the two-dimensional lattice, but on the three-dimensional lattice, it is still not very clear whether or not these models have the same universality. By using a Monte Carlo method with cluster updates and color assignment, we obtain the global phase diagram containing the paramagnetic and ferromagnetic phases. The phase transition between the two phases is second order at 1≤n

Percolation and critical O(n) loop configurations.

We study a percolation problem based on critical loop configurations of the O(n) loop model on the honeycomb lattice. We define dual clusters as groups of sites on the dual triangular lattice that are not separated by a loop, and investigate the bond-percolation properties of these dual clusters. The universal properties at the percolation threshold are argued to match those of Kasteleyn-Fortuin random clusters in the critical Potts model. This relation is checked numerically by means of cluster simulations of several O(n) models in the range 1

Phase transitions of a cluster Ising model.

We study a cluster Ising model with multispin interactions which can be exactly solved in the framework of free fermions. The model can realize topological phases with any integer winding numbers; we study the critical and multicritical behaviors of the phase transitions between these topological phases. For the ordinary critical point, we find that the critical exponent that governs the divergence of the correlation length is ν=1, and the critical exponent that describes the scaling behaviors of the order parameter is ß=ΔN_{w}/8, with ΔN_{w} the difference of the winding numbers of the two phases at the two sides of the critical point. However, these results are not applicable for some multicritical points which have much more complicated behaviors, such as path dependent scaling behaviors and quasicritical behaviors and so forth.

Characterization of the complete chloroplast genome of Festuca sinensis (Gramineae).

The complete chloroplast genome from Festuca sinensis, an important perennial bunchgrass of the Gramineae, is determined in this study. The whole chloroplast genome sequence of F. sinensis has been characterized by Illumina pair-end sequencing. The circular genome is 134,177 bp long, containing a large single-copy region (LSC) of 79,367 bp and a small single-copy region (SSC) of 12,510 bp, which are separated by a pair of 21,150 bp inverted repeat regions (IRs). It encodes a total of 150 genes, including 93 protein-coding genes (75 PCG species), 49 tRNA genes (30 tRNA species) and eight ribosomal RNA genes (4 rRNA species). The most of gene species occur as a single copy, while 30 gene species occur in double copies. The overall A + T content of is 61.6%, while the corresponding values of the LSC, SSC, and IR regions are 63.7, 67.4, and 56.0%, respectively. Phylogenetic analysis suggested that Festuca sinensis was relatively close to Festuca ovina compared with other species of Festuca genera in Gramineae among the species analyzed. This complete chloroplast genome will provide valuable insight into conservation and exploitation efforts for this species as well as useful resources for studying the Gramineae phylogeny.

Overlap of two topological phases in the antiferromagnetic Potts model.

By controlling the vortex core energy, the three-state ferromagnetic Potts model can exhibit two types of topological paradigms, including the quasi-long-range ordered phase and the vortex lattice phase [Phys. Rev. Lett. 116, 097206 (2016)PRLTAO0031-900710.1103/PhysRevLett.116.097206]. Here, using Monte Carlo simulations using an efficient worm algorithm, we show that by controlling the vortex core energy, the antiferromagnetic Potts model can also exhibit the two topological phases, and, more interestingly, the two topological phases can overlap with each other.

Development and characterization of ricinoleic acid-based sulfhydryl thiol and ethyl cellulose blended membranes.

Ethyl cellulose (EC) membranes can be combined with efficient plasticizers derived from renewable resources to form supramolecular systems. In this paper, a novel ricinoleic acid-based sulfhydryl triol (STRA) was first synthesized and used as a plasticizer for EC membranes. A supramolecular membrane of EC and STRA using van der Waals forces was designed. The morphology, hydrophilic performance, thermal stability, and mechanical properties of the composites were investigated. While pure EC is brittle, its membrane ductility and hydrophilic performance can be improved by integration with STRA. The highest tensile strength was found in EC/STRA (90/10) (8.37MPa). Impressively, the EC/STRA(60/40) and EC/STRA(50/50) elongation at break values were 17.4 and 20.2 times higher, respectively, than that of pure EC. This novel ricinoleic acid-based sulfhydryl triol can be used as a feedstock for hydrophobic EC membranes.

Percolation of the site random-cluster model by Monte Carlo method.

We propose a site random-cluster model by introducing an additional cluster weight in the partition function of the traditional site percolation. To simulate the model on a square lattice, we combine the color-assignation and the Swendsen-Wang methods to design a highly efficient cluster algorithm with a small critical slowing-down phenomenon. To verify whether or not it is consistent with the bond random-cluster model, we measure several quantities, such as the wrapping probability Re, the percolating cluster density P∞, and the magnetic susceptibility per site χp, as well as two exponents, such as the thermal exponent yt and the fractal dimension yh of the percolating cluster. We find that for different exponents of cluster weight q=1.5, 2, 2.5, 3, 3.5, and 4, the numerical estimation of the exponents yt and yh are consistent with the theoretical values. The universalities of the site random-cluster model and the bond random-cluster model are completely identical. For larger values of q, we find obvious signatures of the first-order percolation transition by the histograms and the hysteresis loops of percolating cluster density and the energy per site. Our results are helpful for the understanding of the percolation of traditional statistical models.

Ising-like phase transition of an n-component Eulerian face-cubic model.

By means of Monte Carlo simulations and a finite-size scaling analysis, we find a critical line of an n-component Eulerian face-cubic model on the square lattice and the simple cubic lattice in the region v>1, where v is the bond weight. The phase transition belongs to the Ising universality class independent of n. The critical properties of the phase transition can also be captured by the percolation of the complement of the Eulerian graph.

Critical properties of the Hintermann-Merlini model.

Many critical properties of the Hintermann-Merlini model are known exactly through the mapping to the eight-vertex model. Wu [J. Phys. C 8, 2262 (1975)] calculated the spontaneous magnetizations of the model on two sublattices by relating them to the conjectured spontaneous magnetization and polarization of the eight-vertex model, respectively. The latter conjecture remains unproved. In this paper we numerically study the critical properties of the model by means of a finite-size scaling analysis based on transfer matrix calculations and Monte Carlo simulations. All analytic predictions for the model are confirmed by our numerical results. The central charge c=1 is found for the critical manifold investigated. In addition, some unpredicted geometric properties of the model are studied. Fractal dimensions of the largest Ising clusters on two sublattices are determined. The fractal dimension of the largest Ising cluster on the sublattice A takes a fixed value D(a)=1.888(2), while that for sublattice B varies continuously with the parameters of the model.