Enhancing bioretention efficiency for pollutant mitigation in stormwater runoff: Exploring ecosystem cycling dynamics amidst temporal variability.

In this study, three distinct bioretention setups incorporating fillers, plants, and earthworms were established to evaluate the operational efficiency under an ecosystem concept across varying time scales. The results revealed that under short-term operating conditions, extending the drying period led to a notable increase in the removal of NO3--N, total phosphorus (TP), and chemical oxygen demand (COD) by 5 %-7%, 4 %-12 %, and 5 %-10 %, respectively. Conversely, under long-time operating conditions, the introduction of plants resulted in a significant boost in COD removal by 10 %-20 %, while the inclusion of earthworms improved NH4+-N and NO3--N removal, especially TP removal by 9 %-16 %. Microbial community analysis further indicated the favorable impact of the bioretention system on biological nitrogen and phosphorus metabolism, particularly with the incorporation of plants and earthworms. This study provides a reference for the operational performance of bioretention systems on different time scales.

Studies on the Surface Adsorption of Binary Molten Salts.

The surface adsorption of eight binary molten salts, AgNO3-M1NO3(M1 = Li, Na, K, Rb), NaNO3-M2NO3 (M2 = K, Rb), Ca(NO3)2-CsNO3, and Cd(NO3)2-NaNO3, has been investigated. It is found that the surface tension and temperature of molten salts at constant pressure and mole fraction satisfy the same equation as that for pure liquid compounds reported in our previous works. The heats of phase transition from the bulk to the surface phase for eight molten salts are determined. The heats per unit area are all at the order of -10-2 J/m2. The phase transition is exothermic because the entropy in the surface phase is smaller than the entropy in the bulk phase. The ratio of the solute surface concentration to the solute bulk concentration is approximated as the first-order polynomials of the solute bulk concentration. Then, curves of the surface tension vs the solute bulk concentration are well fitted. The ratio (ΔcBs/ΔcBα) is used to interpret the changing trend of the surface tension with bulk concentrations of solute. It is also found that the surface tension of molten salts decreases linearly with the solute surface concentration.

Design and spatial pattern optimization for a sponge city using factor analysis and geographical statistics to restore urban resilience: A case study in a coastal area of China.

The sponge city is a new concept of stormwater management for ecological city construction, which aims to restore water-cycle processes and reduce runoff. Cities in coastal districts are suffering from serious instability due to high population density, urbanization, and land-use changes. However, previous research contains few evaluations of balancing urban ecological indicators of sponge city performance, including geographical, environmental, economic, and social factors, and their effect on resilience at a macro level to develop low-impact development schemes. In this study, we developed an integrated framework using factor analysis, geographical statistics, multi-objective analysis, and remote sensing methods to extract the factors influencing sponge city resilience and to establish spatial pattern schemes. The results indicated that the urbanization degree and plant adaptability had the greatest impact on sponge city performance, with weights of 45 and 27%, respectively. Sponge city spatial pattern schemes performed the best in the combination scenario of 14.8-46.8% green roofs (by area ratio) supported by grooves and rain barrels +10% herbaceous basins divided into units by ecological tree pools +10% permeable pavements and sidewalks. This scenario balanced facilities and cost to optimize the spatial pattern, which improved sponge city adaptability and urban ecological conditions.

Theoretical Perspective on Two-State "ON-OFF" NLO Switch of Rh(III)-Azobenzene Complex with Considerable First Hyperpolarizability.

In this paper, a light-induced Rh(III)-azobenzene (azo) complex in its two conformations (cis- and trans-form) is analyzed via density functional theory methods, focusing on the geometrical and electronic structure, linear and second-order nonlinear optical (NLO) properties, as well as UV-vis absorption spectra. The results show that trans-Rh exhibits more obvious charge separation and more extensive π-conjugation than cis-Rh. The energy gaps (Egap) between the highest occupied molecular orbital and lowest unoccupied molecular orbital of cis-Rh and trans-Rh are as small as 0.28 and 0.36 eV, respectively. The unusual small Egap facilitates electronic transition and accompanies large NLO responses. In particular, cis-Rh and trans-Rh possess considerably large second-order NLO responses with the first hyperpolarizability (ßtot) up to 7.0 × 104 a.u. ("OFF" state) and 8.5 × 104 a.u. ("ON" state), respectively. trans-Rh shows good π-conjugation and obvious electric delocalization relative to cis-Rh and thus a considerable ßtot value. The switchable ratio of ßtot (trans-Rh)/ßtot (cis-Rh) is equal to 1.2, showing switch characteristics. UV-vis analyses indicate that the ON and OFF states can finely tune the absorption range due to the strongest absorption peaks of cis-Rh (301 nm) and trans-Rh (446 nm) lying in the UV and vis region, respectively. It is expected that the studied Rh(III)-azo complexes may be applied in the field of optoelectronics.

Block Effective Hamiltonian Theory and Its Application.

Block effective Hamiltonian theory (BEHT) is presented in this work. Configuration interaction functions are divided into P, Q, and R spaces. Effective Hamiltonian is constructed with the partitioning technique within the P space. The eigenvalue problem of the effective Hamiltonian is then solved iteratively. It is demonstrated that the ground-state energies of N2, HF, and F2 calculated with BEHT converge to the multireference configuration interaction energies from below and the iteration number becomes smaller as BEHT energy becomes closer to the exact energy. The accuracy of BEHT is better than that of the second-order multireference perturbation theory, although the matrix elements in both methods are the same. The ionization potentials of the singlet state of HF, the doublet state of F, and the triplet state of NH and the potential energy curves of CH4, C2, and N2 are calculated with BEHT and compared with experiments and results of CASSCF, CCSD, and CCSD(T) and the results of the full configuration interaction if available. The iteration numbers are all less than 10 in this study. These calculations show the good performances of BEHT in comparison with other theoretical approximation methods.

Computational Studies on the Reactivity of Polycyclic Aromatic Hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) are widely present in the environment as toxic pollutants. In this study, quantum chemistry methods are used to study reactions of PAHs in both particle and gas phases. Seven theoretical methods are exploited to predict the reactive sites of 15 PAHs in the particle phase. Among these methods, the performance of the condensed Fukui function (CFF) is optimum. The gas-phase reactions of eight PAHs are also investigated. Except for fluorene, CFF predicts correctly the gas-phase mono-nitro products for seven systems. The products of fluorene predicted by CFF are 1-nitrofluorene and 3-nitrofluorene, which is however inconsistent with the experimental results. Transition state theory is then used to investigate the reaction mechanism of fluorene. Calculated rate constants for 3-nitrofluorene and 2-nitrofluorene formation are much bigger than that for 1-nitrofluorene formation, which is in agreement with the experimental results.

Ultrastable liquid crystalline blue phase from molecular synergistic self-assembly.

Fabricating functional materials via molecular self-assembly is a promising approach, and precisely controlling the molecular building blocks of nanostructures in the self-assembly process is an essential and challenging task. Blue phase liquid crystals are fascinating self-assembled three-dimensional nanomaterials because of their potential information displays and tuneable photonic applications. However, one of the main obstacles to their applications is their narrow temperature range of a few degrees centigrade, although many prior studies have broadened it to tens via molecular design. In this work, a series of tailored uniaxial rodlike mesogens disfavouring the formation of blue phases are introduced into a blue phase system comprising biaxial dimeric mesogens, a blue phase is observed continuously over a temperature range of 280 °C, and the range remains over 132.0 °C after excluding the frozen glassy state. The findings show that the molecular synergistic self-assembly behavior of biaxial and uniaxial mesogens may play a crucial role in achieving the ultrastable three-dimensional nanostructure of blue phases.

Quantitative description of surface adsorption of surfactant in aqueous solution without the Gibbs equation.

A new equation related to the surface tension and concentration of solute in the surface region is derived and a three-step procedure is proposed to determine the molecular area of surfactants in aqueous solution at saturation of the air-liquid surface. Based on their surface tension data, the molecular areas of hexyl, octyl and decyl trimethylammonium bromide (HTABr, OTABr and DTABr) in aqueous solutions have been calculated and are in agreement with the computational results of density functional theory. Gibbs analysis has also been carried out for these surfactants. As the surface tension data are fitted with the Gibbs equation, it is found that there exist two line segments for both OTABr and DTABr, which lead to two molecular areas for each of them. This arbitrariness indicates that no unique molecular area could be obtained for OTABr and DTABr. As for HTABr, its molecular area obtained with Gibbs analysis is out of the range estimated with density functional theory. These results show the failure of the Gibbs equation.

Rhodium-Catalyzed C(sp2)-H Amidation of Azine with Sulfonamides.

Direct C-H amidation of azine with sulfonamide was developed for the first time. The reactions proceeded smoothly under benign conditions and gave the corresponding products with high selectivity. This approach shows high regioselectivity, wide substrate scope, and functional group tolerance. Additionally, this transformation can also be scaled up to the gram level. This strategy allows for the direct preparation of ortho-sulfonamide-substituted ketone products, thus providing a good complement to previous C-H amidation.

Multireference Rayleigh-Schrödinger perturbation theory and its application.

Based on the complete active space multireference wavefunction, multireference Rayleigh-Schrödinger perturbation theory (MRSPT) is derived with the assumption that the orbital energies of active orbitals are the same as ε¯, an unknown parameter. In this work, ε¯ is optimized at the MRSPT2 level. The second and third order perturbation theories are shown numerically to be size extensive. The second order perturbation theory is exploited to compute the ground state energies of F2, AlH, HCl, and P2 and to optimize the equilibrium bond lengths and harmonic vibrational frequencies of BH, BF, P2, HF, and F2. The dissociation behaviors of NH3 and OH- have also been investigated. Comparisons with other theoretical models as well as the experimental data have been made to show advantages of the present theory.

Broadband Reflection in Polymer-Stabilized Cholesteric Liquid Crystals via Thiol-Acrylate Chemistry.

Thiols are prone to react with a multitude of various functional groups in high yields, which has been widely used for surface- and particle-patterning, bioorganic synthesis, polymer modification, imprint nanolithography, the fabrication of optical components, hydrogel synthesis, and the curing of hard protective coatings. In this work, a chiral thiol with a high helical twisting power was synthesized through a novel synthetic route with high selectivity, yield, and cost-effectiveness. It was then used to fabricate a liquid-crystal composite film with ultra-wide broadband reflection via thiol click chemistry. Cholesteric liquid-crystal materials with broadband reflection have many potential applications for broadband polarizers, polarizer-free displays, organic optical data storage media, smart switchable reflective windows, and continuous waveband laser protection.

Nonelectric Sustaining Bistable Polymer Framework Liquid Crystal Films with a Novel Semirigid Polymer Matrix.

In this work, a bistable polymer framework liquid crystal (PFLC) thin film by thermal curing of epoxy monomers with two different thiols, a traditional flexible-structure thiol and a novel original rigid-structure thiol, has been successfully fabricated, combining a novel mixed morphology of polymer matrix and cholesteric liquid crystals with negative dielectric anisotropy. The polymer framework morphology has been formed by curing two types of epoxy monomers with two types of thiols, and the liquid crystals tend to be focal conic textures with large size domains at the initial state in the PFLC film so that it has a moderate light transmissivity at this state between the transparent state and the opaque state. Thus, the devices based on PFLC films can be switched reversibly between the transparent state and the opaque state by alternative electric field. In addition, the states can be sustained after the electric field is removed. The bistable memory effect comes from the anchoring effects of the polymer frameworks with a novel morphology in the microdomains of the PFLCs. Therefore, the optimized bistable PFLC film keeps its initial state without external electric field and any other energy consumption for a long time after altering the state by applying an instant electric field. The special polymer frameworks in the bistable PFLC films endow the films with excellent electro-optical properties and mechanical properties. The devices are energy-efficient and cost-saving and have great potential applications in energy-efficient reflective displays, electronic papers, writing tablets, and smart windows.

A Facile All-Solution-Processed Surface with High Water Contact Angle and High Water Adhesive Force.

A series of sticky superhydrophobicity surfaces with high water contact angle and high water adhesive force is facilely prepared via an all-solution-processed method based on polymerization-induced phase separation between liquid crystals (LCs) and epoxy resin, which produces layers of epoxy microspheres (EMSs) with nanofolds on the surface of a substrate. The morphologies and size distributions of EMSs are confirmed by scanning electron microscopy. Results reveal that the obtained EMS coated-surface exhibits high apparent contact angle of 152.0° and high water adhesive force up to 117.6 µN. By varying the composition of the sample or preparing conditions, the sizes of the produced EMSs can be artificially regulated and, thus, control the wetting properties and water adhesive behaviors. Also, the sticky superhydrophobic surface exhibits excellent chemical stability, as well as long-term durability. Water droplet transportation experiments further prove that the as-made surface can be effectively used as a mechanical hand for water transportation applications. Based on this, it is believed that the simple method proposed in this paper will pave a new way for producing a sticky superhydrophobic surface and obtain a wide range of use.

A new size extensive multireference perturbation theory.

A new multireference perturbation series is derived based on the Rayleigh-Schrödinger perturbation theory. It is orbitally invariant. Its computational cost is comparable to the single reference Møller-Plesset perturbation theory. It is demonstrated numerically that the present multireference second- and third-order energies are size extensive by two types of supermolecules composed of H2 and BH monomers. Spectroscopic constants of F2(X1Σg+),Cl2(X1Σg+),C2-(X2Σg+),B2(X3Σg-),and C2+(X4Σg-) as well as the ground state energies of H2O, NH2, and CH2 at three bond lengths have been calculated with the second multireference perturbation theory. The dissociation behaviors of CH4 and HF have also been investigated. Comparisons with other approximate theoretical models as well as the experimental data have been carried out to show their relative performances.

Revealing the nature of intermolecular interaction and configurational preference of the nonpolar molecular dimers (H2)2, (N2)2, and (H2)(N2).

Understanding the nature of noncovalent interactions between nonpolar small molecules is not only theoretically interesting but also important for practical purposes. The interaction mechanism of three prototype dimers (H2)2, (N2)2, and (H2)(N2) are investigated by state-of-the-art quantum chemistry calculations and energy decomposition analysis. It is shown that their configuration preferences are essentially controlled by the electrostatic component rather than the dispersion effect though the monomers have zero dipole moment. These configuration preferences can also be fairly well and conveniently interpreted by visually examining the electrostatic potential map.

Bond order analysis based on the Laplacian of electron density in fuzzy overlap space.

Bond order is an important concept for understanding the nature of a chemical bond. In this work, we propose a novel definition of bond order, called the Laplacian bond order (LBO), which is defined as a scaled integral of negative parts of the Laplacian of electron density in fuzzy overlap space. Many remarkable features of LBO are exemplified by numerous structurally diverse molecules. It is shown that LBO has a direct correlation with the bond polarity, the bond dissociation energy, and the bond vibrational frequency. The dissociation behavior of LBO of the N-N bond in N2 has been studied. Effects of the basis sets, theoretic methods, and geometrical conformations on LBO have also been investigated. Through comparisons, we discussed in details similarities and discrepancies among LBO, Mayer bond order, natural localized molecular orbital bond order, fuzzy overlap population, and electron density at bond critical points.

Quantitative analysis of molecular surface based on improved Marching Tetrahedra algorithm.

Quantitative analysis of molecular surface is a valuable technique for analyzing non-covalent interaction, studying molecular recognition mode, predicting reactive site and reactivity. An efficient way to realize the analysis was first proposed by Bulat et al. (J. Mol. Model., 16, 1679), in which Marching Tetrahedra (MT) approach commonly used in computer graphics is employed to generate vertices on molecular surface. However, it has been found that the computations of the electrostatic potential in the MT vertices are very expensive and some artificial surface extremes will be presented due to the uneven distribution of MT vertices. In this article, we propose a simple and reliable method to eliminate these unreasonably distributed surface vertices generated in the original MT. This treatment can save more than 60% of total analysis time of electrostatic potential, yet the loss in accuracy is almost negligible. The artificial surface extremes are also largely avoided as a byproduct of this algorithm. In addition, the bisection iteration procedure has been exploited to improve accuracy of linear interpolation in MT. The most appropriate grid spacing for surface analysis has also been investigated. 0.25 and 0.20 bohr are recommended to be used for surface analysis of electrostatic potential and average local ionization energy, respectively.

Multiwfn: a multifunctional wavefunction analyzer.

Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5) Plot density-of-states and spectrum. (6) Topology analysis for electron density. Some other useful utilities involved in quantum chemistry studies are also provided. The built-in graph module enables the results of wavefunction analysis to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com.

A Single Reference Perturbation Theory beyond the Møller-Plesset Partition.

A new single reference perturbation partition is proposed for restricted open-shell Hartree-Fock (ROHF) and complete active space self-consistent field (CASSCF) orbitals. It is a sum of one-particle operator which is implicitly defined. When the operator acts on a ROHF or CASSCF orbital, the resultant eigenvalue is the orbital's corresponding orbital energy coming from the ROHF or CASSCF calculation. HF, F2, and N2 with stretched bonds are used for the size extensivity test. Results indicate that the first three-order energies calculated with the new partition are size extensive. Single reference perturbation calculations for H2O, NH3, and CH4 with CASSCF orbitals have been performed and compared with other methods like MRCI, MRCI+Q, MRPT2, and MRPT3. The single reference nature of the present perturbation theory is also shown with computations of the singlet-triplet separation of the CH2 and SiH2 radicals.

Cation electric field is related to hydration energy.

Electronic structure calculations on ions that use dielectric continuum theory to mimic solvent around the bare ionic solutes are often prone to make large errors in the hydration energies. It is found for cations that much of the error can be accounted for by a simple linear correlation with the maximum value found anywhere on the dielectric cavity surface of the solute potential or, even better, the outgoing normal electric field, thus mirroring analogous results previously obtained for anions. This correlation allows for significantly improved estimates of cation hydration energies while still retaining cavities of physically reasonable size in determination of the bulk dielectric contributions.