Why the abnormal phenomena of D-band center theory exist?A new BASED theory for surface catalysis and chemistry

Since the D-band center theory was proposed,it has been widely used in the fields of surface chemistry by almost all researchers,due to its easy understanding,convenient operation and relative accuracy.However,with the continuous development of material systems and modification strategies,researchers have gradually found that D-band center theory is usually effective for large metal particle systems,but for small metal particle systems or semiconductors,such as single atom systems,the opposite conclusion to the D-band center theory is often obtained.To solve the issue above,here we propose a bonding and anti-bonding orbitals stable electron intensity difference(BASED)theory for surface chemistry.The newly-proposed BASED theory can not only successfully explain the abnormal phenomena of D-band center theory,but also exhibits a higher accuracy for prediction of adsorption energy and bond length of intermediates on active sites.Importantly,a new phenomenon of the spin transition state in the adsorption process is observed based on the BASED theory,where the active center atom usually yields an unstable high spin transition state to enhance its adsorption capability in the adsorption process of intermediates when their distance is about 2.5Å.In short,the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.

Density Functional Theory Calculations on Ni-Ligand Bond Dissociation Enthalpies

The formation and breaking of Ni-L （L=N-heterocyclic carbene, tertiary phosphine etc.） bond is involved in many Ni-catalyzed/mediated reactions. The accurate prediction of Ni-L bond dissociation enthalpies （BDEs） is potentially important to understand these Ni-complex involving reactions. We assess the accuracy of diffierent DFT functionals （such as B3LYP, M06, MPWB1K, etc.） and diffierent basis sets, including both effective core potentials for Ni and the all electron basis sets for all other atoms in predicting the Ni-L BDE values reported recently by Nolan et al. [J. Am. Chem. Soc. 125, 10490 （2003） and Organometallics 27, 3181 （2008）]. It is found that the MPWB1K/LanL2DZ：6-31＋G（d,p）//MPWB1K/LanL2DZ：6-31G（d） method gives the best correlations with the experimental results. Meanwhile, the solvent effect calculations （with CPCM, PCM, and SMD models） indicate that both CPCM and PCM perform well.

MACRO SLIP THEORY OF PLASTICITY FOR POLYCRYSTALLINE SOLIDS

A macro slip theory is presented in this paper.Four independent slip systems are proposed for polycrystalline solids.Each slip system consists of a slip plane which lies on a face of the octahedron in stress space and a slip direction which is coincident with shear stress acting on the same face of the octahedron.It is proved that for proportional loading,present results are identical with the classical flow theory of plasticity. For nonproportional loading,the macro slip theory shows good predicting ability.The calculated results are in good agreement with the experimental data.

Construction of improved rigid blocks failure mechanism for ultimate bearing capacity calculation based on slip-line field theory

Based on the slip-line field theory, a two-dimensional slip failure mechanism with mesh-like rigid block system was constructed to analyze the ultimate bearing capacity problems of rough foundation within the framework of the upper bound limit analysis theorem. In the velocity discontinuities in transition area, the velocity changes in radial and tangent directions are allowed. The objective functions of the stability problems of geotechnical structures are obtained by equating the work rate of external force to internal dissipation along the velocity discontinuities, and then the objective functions are transformed as an upper-bound mathematic optimization model. The upper bound solutions for the objective functions are obtained by use of the nonlinear sequential quadratic programming and interior point method. From the numerical results and comparative analysis, it can be seen that the method presented in this work gives better calculation results than existing upper bound methods and can be used to establish the more accurate plastic collapse load for the ultimate bearing capacity of rough foundation.

New observations on hydrogen bonding in ice by density functional theory simulations

In this paper, we report on a series of computational simulations on hydrogen bonding in two ice phases （Ih and Ic） using CASTEP with PW91 and RPBE exchange-correlation based on ab initio density functional theory. The strength of the H-bond is correlated with intramolecular O-H stretching, and the energy splitting exists for both the H-bond and covalent O-H stretching. By analyzing the dispersion relationship of to（q）, we observe the separation of the longitudinal optic （LO） mode from transverse optic （TO） mode at the gamma point, seemingly interpreting the controversial two H-bond peaks in the vibrational spectrum of ice recorded by inelastic incoherent neutron scattering experiments. The test of ambient environment on phonon density of sates （PDOS） shows that the relaxed tetrahedral structure is the most stable structural configuration for water clusters.

Theoretical Study of the N-NO_2 Bond Dissociation Energies for Energetic Materials with Density Functional Theory

The N-NO2 bond dissociation energies （BDEs） for 7 energetic materials were computed by means of accurate density functional theory （B3LYP, B3PW91 and B3P86） with 6-31G＊＊ and 6-311G＊＊ basis sets. By comparing the computed energies and experimental results, we find that the B3P86/6-311G＊＊ method can give good results of BDE, which has the mean absolute deviation of 1.30kcal/mol. In addition, substituent effects were also taken into account. It is noted that the Hammett constants of substituent groups are related to the BDEs of the N-NO2 bond and the bond dissociation energies of the energetic materials studied decrease when increasing the number of NO2 group.

Bonding stress—slip constitutive behavior between bars and grout concrete

To establish bonding stress—slip constitutive model between bars and grout concrete,13 test specimens were employed to study the bonding behavior and the force transfer of bars adhered to grout concrete. The bonding stress development of bars adhered to grout concrete was analyzed. The local bonding stress—slip curve was obtained. Based on the test results,a new bonding stress— slip constitutive model between bars and grout concrete was proposed. The results show that the maximum bonding stress is not influenced by the bar bond length,but it is strengthened when the splitting strength of grout concrete is increased. The model matches the experimental results well,and the regressing coefficient equals 1.7.

Bond-slip constitutive relationship between bars and mortar for block masonry

Ten specimens were tested in this paper in order to study the bond behavior and the process of force transfer when bars adhered to mortar. The development of the bond stress between bars and mortar was calculated. Test results show that the maximum bond-stress is not influenced by the bar bond length and increases as the increased splitting strength of mortar for block. The local bond stress-slip curve was obtained. Then,based on the regressive analysis of test data,two bond shearing stress-slip constitutive models between bars and mortar were proposed. The models can be used in the numerical simulation or finite element analysis and provide references for the improvement of the corresponding design codes.

Research on Bond-Slip Constitutive Relation for Steel Reinforced Concrete Members

The constitutive relation of bond-slip on steel and concrete interface is proposed for short steel reinforced concrete （SRC） column. Based on the experimental research on bond-slip performance, a mechanical model of short SRC column in pulling or pushing test is established. By means of the elasto-plasticity theory the explicit formulation of bond-slip constitutive relation τ-s in different anchor-hold place of push and pull member is investigated under the conditions of balance and boundary. The study shows that the constitutive relation is relevant to the embedment length and the thickness of concrete cover. The results are continuous descriptions of bond-slip constitutive relation and can be used to analyze the non-linear performance of SRC members. Results indicate that the principle of the method is correct and it performs well for short SRC column.

Stress Variation Model of Bond Stress-Slip Relationship Between Steel Bar and Concrete

-Based on the experimental data, a stress variation model of the bond stress-slip relationship between steel bar and concrete is established. The characteristic of the model is that the boundary conditions are satisfied very well; the effects of the material properties, the concrete cover, the crack spacing and the distance from the cracked cross section are considered. Good agreement between measured and calculated bond stress-slip relationship is found. This model is useful for the study of the stiffness, deformation and crack width of reinforced concrete members, and for the nonlinear analysis of reinforced concrete structures by the finite element method.

A New Group Theoretical Approach to the Nonorthogonal Problem in Valence Bond Theory

Introduction There has been a very significarnt resurgence of interest in ab initio valence bond calculations recently. This is because the VB calculation based on nonorthogonal basis can provide intuitive understanding about many very important phenomena in chemistry. However, practical calculation based on nonorthogonal basis is still a great challenge even to deal with a quite small system due to the well-known N! (or

Theoretical Investigation of the Bonding Properties of Bis（glycinato） d8metal（II） Dihydrate Complexes Using Density Functional Theory

Density functional theory （DFT） approach has been applied for the analysis of the bond between the [（H20）2] and the [M（gly）2] fragments in a series of trans and cis [M（gly）2[（H20）2] complexes. For comparative purpose, both relativistic and non-relativistic calculations have been performed. The nature of the interaction between the [（H20）2] and [M（gly）2] fragments was investigated using energy decomposition analysis, Hirshfeld atomic charge variation, molecular orbital considerations and bond order decomposition analysis, respectively. Results reveal that the [（H20）：]-[M（gly）2] interaction lies from the hydrogen bridge interaction between these fragments. The strength of the bonding increases in the order Ni2＋ 〉 Pd2＋ 〉 Pt2＋ while the relativistic correction tends to strengthen the [（H2O）2---[M（gly）2] bond in the order Ni 〈 Pd 〈 Pt.

A High-Precision Calculation of Bond Length and Spectroscopic Constants of Hg2 Based on the Coupled-Cluster Theory with Spin-Orbit Coupling

Based on the two-component relativistic effective core potential and matched basis sets cc-pwcvnz-pp （n=Q, 5）, combining the completed basis-set extrapolation of electronic correlation energy and the fourth-order polynomial fitting technique, the bond length and spectroscopic constants of Hg2 are studied by the coupled cluster theory with spin-orbit coupling. Spin-orbit coupling is included in the post Hartree-Fock procedure, i.e., in the coupled- cluster iteration, to obtain more reliable theoretical results. The results show that our theoretical values agree with the experimental values very well and will be helpful to understand the spectral character of Hg2.

Density Functional Theory Study of Marine Polybrominated Diphenyl Ethers in Anaerobic Degradation

Polybrominated diphenyl ethers(PBDEs)are a kind of serious pollutants in the ocean.Biodegradation is considered as an economical and safe way for PBDEs removal and reductive debromination dominates the initial pathway of anaerobic degradation.On the basis of experimental study,Octa-BDE 197,Hepta-BDE 183,Hexa-BDE 153,Penta-BDE 99 and Tetra-BDE 47 were selected as the initial degradation objects,and their debromination degradation were studied using density functional theory.The structures were optimized by Gaussian 09 program.Furthermore,the molecular orbitals and charge distribution were analyzed.All C-Br bond dissociation energies at different positions including ortho,meta and para bromine atoms were calculated and the sequence of debromination was obtained.There is a close relationship between molecular structure,charge,molecular orbital and C-Br bond.All PBDEs exhibited similar debromination pathways with preferential removal of meta and para bromines.

氯盐环境下UHPC-NC界面黏结性能试验研究

氯盐环境作为一种较为常见的化学侵蚀环境,研究其对超高性能混凝土(ultra-high performance concrete,UHPC)和普通混凝土(normal concrete,NC)界面耐久性能的影响对于UHPC加固混凝土结构和UHPC-NC组合结构的工程应用均具有重大的现实意义.基于此,通过在常规环境以及氯盐环境下的推出试验,获得了干湿循环次数(0次、25次、50次)、氯盐浸泡天数(0 d、50 d、100 d)及界面处理方式(钢丝刷刷毛、高压水射流冲毛、表面缓凝处理)对UHPC-NC界面黏结强度、界面黏结刚度及界面黏结滑移曲线的影响.结果表明:在100 d试验周期内,干湿循环及氯盐浸泡作用造成的界面黏结强度损失率不超过20%;氯盐环境作用时长的增加会导致界面黏结刚度的降低;随着界面粗糙度的增加,UHPC-NC试件的界面黏结强度以及界面黏结刚度均会增加;界面粗糙度的提高有助于界面抗氯盐侵蚀能力的提升.受到界面处理方法的影响,UHPC-NC试件经历干湿循环及氯盐浸泡后,荷载滑移曲线呈现2种不同的形式,分别对应光滑界面(钢丝刷刷毛界面)和其他界面(高压水射流冲毛界面和缓凝剂处理界面).各组试件的黏结滑移曲线在荷载到达峰值前趋于一致;荷载到达峰值后,前者存在荷载骤降段及持荷段,后者则随着滑移量的增加荷载不断降低.根据UHPC-NC黏结滑移曲线特征,提出了黏结滑移建议模型.

平台场域内中等收入人群“滑落”风险形成与治理机制——基于美团外卖骑手的案例研究

在中等收入人群绝对规模增加的过程中,也存在着“滑落”现象,以往对于中等收入人群的研究多从收入分配制度、人力资本等角度展开。通过美团案例的研究发现,中等收入人群“滑落”的根源为生态成员权责范围的模糊,“稳中”还需依赖平台治理。处于市场优势地位的美团,在供求失衡的市场机制和算法技术的支持下,通过灵活用工模式规避雇佣责任,但这种劳资关系并非稳定的和可持续的。外卖骑手可以通过自我赋能、维护自身主体性、多栖战略等途径抵御“滑落”,同时,制度缺口填补、平台与政府协同治理、平台企业垄断规制和多元主体赋权的方式也可以阻断外卖骑手的“滑落”通道。外卖骑手“滑落”是研究橄榄型社会结构构建的经典案例,对我国完善平台治理结构和发展共同富裕具有积极意义。

BFRP筋回收轮胎钢纤维混凝土黏结性能分析

对玄武岩纤维增强复合材料(BFRP)筋在回收轮胎钢纤维(RTSF)混凝土中的黏结性能进行了试验和分析研究.对不同RTSF体积掺量、BFRP筋直径和嵌入长度的试件进行了拉拔试验,研究其对黏结破坏模式、黏结滑移响应和黏结强度的影响,并提出了BFRP筋RTSF混凝土的黏结滑移理论模型.结果表明:BFRP筋RTSF混凝土黏结破坏类型包括拔出破坏、劈裂破坏以及拔出且劈裂破坏;BFRP筋直径对黏结破坏模式无显著影响,而RTSF体积掺量、BFRP筋直径和嵌入长度均对黏结强度有较大影响,且RTSF体积掺量与极限黏结强度呈正相关,BFRP筋直径和嵌入长度对其影响与之相反;当RTSF体积掺量从0增大至1.5%时,其极限黏结强度最大可提高约23.87%.与已有模型相比,所提出的黏结滑移理论模型对BFRP筋RTSF混凝土的黏结滑移曲线具有更高的拟合精度.

锚杆岩体界面载荷传递规律及锚固长度设计

为揭示巷道围岩锚固界面脱粘失效机理,量化锚杆支护设计参数,采用三线性粘结滑移模型进行理论分析,对轴向载荷作用下锚固脱粘失效全过程中,锚固段界面剪应力、锚杆轴力分布演化规律以及界面极限锚固力进行研究,根据锚固段长度不同,得到两种界面剪应力分布演化类型。研究结果表明:当锚固长度较短时,界面剪应力存在全长软化阶段;当锚固长度较长时,界面剪应力存在弹性-软化-滑移三段共存阶段。锚固粘结界面弹性段、软化段、摩擦段内的剪应力分别呈现双曲余弦函数衰减分布、余弦函数上升分布、均匀分布规律,锚杆轴力随界面剪应力分布演化呈现多种形态的衰减分布规律。根据锚固界面模型解析计算获得极限锚固力,当不考虑脱粘摩擦力时,极限锚固力随锚固长度的增加趋近于某一固定值;当考虑脱粘摩擦力时,增加锚固长度能够持续提高锚固界面安全系数。研究成果可为锚固机制分析、锚杆支护参数设计提供理论参考。

高强钢管超高性能混凝土界面黏结滑移性能试验

目的为了研究高强钢管超高性能混凝土的黏结滑移性能,方法考虑径厚比、长径比和钢纤维掺量3个参数的影响,设计并制作15根构件进行试验研究,通过推出试验,得到轴向荷载与加载端位移的荷载-位移曲线,以及高强钢管与超高性能混凝土之间的黏结强度,根据试验结果,对影响黏结强度的参数进行定性定量分析。结果结果表明:随着高强钢管长径比和径厚比的增加,黏结强度减小;随着钢纤维掺量增加,试件黏结强度先增加后减小,即当钢纤维掺量从1%增加到2%时,黏结强度增加,但当钢纤维掺量从2%增加到3%时,黏结强度反而降低;试件荷载-滑移曲线表现为两种形式,一是有明显的峰值点,峰值点后曲线急速下降(部分出现尾部上升的现象),二是曲线无明显峰值点,拐点后曲线持续缓慢增长。高强钢管超高性能混凝土的黏结破坏分为黏结阶段、滑动阶段和抗摩擦阶段。结论以长径比、径厚比、含钢率和套箍系数为参数,结合试验数据并对其进行回归分析,得到适用于高强钢管超高性能混凝土黏结强度的计算模型,并将计算结果与试验结果进行对比,计算值与试验值吻合较好,可为实际工程提供一定参考。