Theoretical Study of the C-CI Bond Dissociation Enthalpy and Electronic Structure of Substituted Chlorobenzene Compounds

Quantum chemical calculations were used to estimate the bond dissociation energies （BDEs） for 13 substituted chlorobenzene compounds. These compounds were studied by the hybrid density functional theory （B3LYP, B3PW91, B3P86） methods together with 6-31G^＊＊ and 6-311G^＊＊ basis sets. The results show that B3P86/6-311G^＊＊ method is the best method to compute the reliable BDEs for substituted chlorobenzene compounds which contain the C-C1 bond. It is found that the C-C1 BDE depends strongly on the computational method and the basis sets used. Substituent effect on the C-C1 BDE of substituted chlorobenzene compounds is further discussed. It is noted that the effects of substitution on the C-C1 BDE of substituted chlorobenzene compounds are very insignificant. The energy gaps between the HOMO and LUMO of studied compounds estimate the relative thermal stability ordering are also investigated and from this data we of substituted chlorobenzene compounds.

Structures and Thermodynamic Properties of HCOCl-HOCl Complexes

B3LYP/6-311＋＋G level were employed to obtain the optimized geometries and calculated frequency of HCOCl and HOCl complexes.Five stable isomers were obtained,and the one with ClO-H…O=C hydrogen bond was the most stable among five stable isomers,the BSSE and ZPE corrected interaction energy were of-11.92 kJ/mol.The formation of hydrogen bonds made the H―O stretching modes of complexes red-shifted relative to that of the monomer.At 298.15 K and standard state,the formations of stable complexes were an exothermic and non-spontaneous process.

Inverse Halogen Bonds Interactions Involving Br Atom in the Electronic Deficiency Systems of CH3＋… Br-Y （Y--H, CCH, CN, NC）

Inverse halogen bonds interactions involving Br in the electronic deficiency systems of CH3＋...Br-Y （Y=H, CCH, CN, NC） have been investigated by B3LYP/6- 311＋＋G（d, p） and MP2/6-311＋＋G（d, p） methods. The calculated interaction energies with basis set super-position error correction of the four IXBs complexes are 218.87, 219.48, 159.18, and 143.05kJ/mol （MP2/6-311＋＋G（d, p））, respectively. The relative stabilities of the four complexes increased in the order： CH3＋ … BrCN〈CH3＋…- BrNC〈CH3＋… BrH≈CH3＋ …BrCCH. Natural bond orbital theory analysis and the chemical shifts calculation of the related atoms revealed that the charges flow from Br-Y to CH3e. Here, the Br of Br-Y acts as both a halogen bond donor and an electron donor. Therefore, compared with conventional halogen bonds, the IXBs complexes formed between Br-Y and CH3＋. Atoms-in-molecules theory has been used to investigate the topological properties of the critical points of the four IXBs structures which have more covalent content.

Key parameter optimization and analysis of stochastic seismic inversion

Stochastic seismic inversion is the combination of geostatistics and seismic inversion technology which integrates information from seismic records, well logs, and geostatistics into a posterior probability density function （PDF） of subsurface models. The Markov chain Monte Carlo （MCMC） method is used to sample the posterior PDF and the subsurface model characteristics can be inferred by analyzing a set of the posterior PDF samples. In this paper, we first introduce the stochastic seismic inversion theory, discuss and analyze the four key parameters： seismic data signal-to-noise ratio （S/N）, variogram, the posterior PDF sample number, and well density, and propose the optimum selection of these parameters. The analysis results show that seismic data S/N adjusts the compromise between the influence of the seismic data and geostatistics on the inversion results, the variogram controls the smoothness of the inversion results, the posterior PDF sample number determines the reliability of the statistical characteristics derived from the samples, and well density influences the inversion uncertainty. Finally, the comparison between the stochastic seismic inversion and the deterministic model based seismic inversion indicates that the stochastic seismic inversion can provide more reliable information of the subsurface character.

电话机巧设“密”键锁长途

本人曾经给多台普通按键式电话机设置了“密”键,给用户解除了被他人侵扰打长话的后顾之忧。已经有机械式长途锁的电话机,设置进密键后可以取消用钥匙开锁的麻烦。这种方法简单、实用、保密不妨一试。密键的设置原理:在原来拨“0”键的电路中串联接入另一个按键,即“密”键。这时单独按“0”键拨号时“0”

Chemical bonding and elastic properties of quaternary arsenide oxides YZnAsO and LaZnAsO investigated by first principles

The structural parameters, chemical bonding and elastic properties of the tetragonal phase quaternary arsenide oxides YZnAsO and LaZnAsO were investigated by using density-functional theory （DFT） within generalized gradient approximation （GGA）. The GGA calculated structural parameters are in agreement with the experimental results. Population analysis suggests that the chemical bonding in YZnAsO and LaZnAsO can be classified as a mixture of ionic and covalent characteristic. Single-crystal elastic constants were calculated and the polycrystalline elastic modules were estimated according to Voigt, Reuss and Hill＇s approximations （VRH）. The result shows that both YZnAsO and LaZnAsO are relatively soft materials exhibiting ductile behavior. The calculated polycrystalline elastic anisotropy result shows that LaZnAsO is more anisotropy in compressibility and YZnAsO is more anisotropy in shear.

Assessment of Contemporary Theoretical Methods for Bond Dissociation Enthalpies

The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the computational cost and higher precision to the best for large systems. The performance of DFT, double-hybrid DFT, and high-level com- posite methods are examined. The tested sets contain monocyclic and polycyclic aromatic molecules, branched hydrocarbons, small inorganic molecules, etc. The results show that the mPW2PLYP and G4MP2 methods achieve reasonable agreement with the benchmark val- ues for most tested molecules, and the mean absolute deviations are 2.43 and 1.96 kcal/mol after excluding the BDEs of branched hydrocarbons. We recommend the G4MP2 is the most appropriate method for small systems （atoms number≤20）; the double-hybrid DFT methods are advised for large aromatic molecules in medium size （20≤atoms number≤50）, and the double-hybrid DFT methods with empirical dispersion correction are recommended for long-chain and branched hydrocarbons in the same size scope; the DFT methods are ad- vised to apply for large systems （atoms number〉50）, and the M06-2X and B3P86 methods are also favorable. Moreover, the differences of optimized geometry of different methods are discussed and the effects of basis sets for various methods are investigated.

The New Enhanced Simple Authenticated Key Agreement Algorithm

Simple authenticated key agrcement algorithm is one of the Diffie-Hellman key agreement variations. It prevents man-inthe-middle attack with only two more packets required to agree on the secret session key, but it has some weaknesses. In this paper, a new enhanced simple authenticated key agreement algorithm is proposed to overcome these weaknesses on the basis of analyzing the weaknesses of the related protocols. The new enhanced simple authenticated key agreement algorithm can get over replay attack and password guessing attack, provide perfect forward secrecy, and hold the merits of the simple authenticated key agreement algorithm.

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.

Density Functional Theory Study for Adsorption of Oxygen and Water Molecules on 6H-SiC(0001) Surface

6H-SiC is an important semiconductor material. The 6H-SiC wafer is always exposed to a high-humidity environment and the effect from the absorbed water molecule and some relative adsorbates is not negligible. Here, the oxygen and water molecules absorbed on the 6H-SiC(0001) surface and the dissociation process were studied with density functional theory. On the 6H-SiC(0001) surface, absorbed O2 is spontaneously dissociated into O*, which is absorbed on a hollow site, and further transforms the 6H-SiC(0001) surface into SiO2. The absorbed H2O is spontaneously broken into OH*and H*, which are both absorbed on the top of the Si atom, and OH* is further reversibly transformed into O* and H*. The H* could saturate the dangling Si bond and change the absorption type of O*, which could stabilize the 6H-SiC(0001) surface and prevent it from transforming into SiO2.

Designer Mg-Mg and Zn-Zn Single Bonds Facilitated by Double Aromaticity in the M2B7^-(M=Mg,Zn)Clusters

The simple homodinuclear M-M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s2electronic configurations,consequently,a dicationic prototype is often utilized to design the M^+-M^+single bond.Existing studies generally use sterically bulky organic ligands L^-to synthesize the compounds in the L^--M^+-M^+-L-manner.However,here we report the design of Mg-Mg and Zn-Zn single bonds in two ligandless clusters,Mg2B7-and Zn2B7-,using density functional theory methods.The global minima of both of the clusters are in the form of M2^2+(B7^3-),where the M-M single bonds are positioned above a quasi-planar hexagonal B7 moiety.Chemical bonding analyses further confirm the existence of Mg-Mg and Zn-Zn single bonds in these clusters,which are driven by the unusually stable B7^3-moiety that is bothσandπaromatic.Vertical detachment energies of Mg2B7-and Zn2B7-are calculated to be 2.79 e V and 2.94 e V,respectively,for the future comparisons with experimental data.

H2O molecule adsorption on s-triazine-based g-C3N4

The interaction between a gas molecule and photocatalyst is vital to trigger photocatalytic reaction.The surface state of photocatalyst affects much in this interaction.Herein,adsorption of H2O molecules on s-triazine-based g-C3N4 was thoroughly studied by first-principle calculation.Although various initial adsorption models with multifarious locations of H2O molecules were built,the optimized models with strong adsorption energy pointed to the same adsorption configuration,in which the H2O molecule hold an upright orientation above the corrugated g-C3N4 monolayer.An intermolecular O-H…N hydrogen bond formed via the binding of a polar O-H bond in H2O molecule and a two-coordinated electron-rich nitrogen atom in g-C3N4.Under the bridging effect of this intermolecular hydrogen bond,electrons would transfer from g-C3N4 to the H2O molecule,thereby lowering the Fermi level and enlarging work function of g-C3N4.Interestingly,regardless of the substitute,i.e.g-C3N4 multilayer,large supercell and nanotube,this adsorption system was highly reproducible,as its geometry structure and electronic property remained unchanged.In addition,the effect of nonmetal element doping on adsorption energy was explored.This work not only disclosed a highly preferential H2O adsorbed g-C3N4 architecture established by intermolecular hydrogen bond,but also contributed to the deep understanding and optimized design in water-splitting process on g-C3N4-based photocatalysts.

Assessment of Advanced xDH@B3LYP Methods in Describing Various Potential Energy Curves Driven byπ-π,CH/π,and SH/πNon-Bonded Interactions

Accurate description of potential energy curves driven by nonbonded interactions remains a great challenge for pure density functional approximations(DFAs).It is because the Rdecay behavior of dispersion cannot be intrinsically captured by the(semi)-local ingredients and the exact-exchange used in the popular hybrid DFAs.Overemphasizing the accuracy on the equilibrium region for the functional construction would likely deteriorate the overall performance on the other regions of potential energy surfaces.In consequence,the empirical dispersion correction becomes the standard component in DFAs to treat the non-bonded interactions.In this Letter,we demonstrate that without the use of empirical dispersion correction,doubly hybrid approximations,in particular two recently proposed rev XYG3 and XYG7 functionals,hold the promise to have a balanced description of non-bonded interactions on the whole potential energy curves for several prototypes ofπ-π,CH/π,and SH/πinteractions.The error of rev XYG3 and XYG7 for non-bonded interactions is around 0.1 kcal/mol,and their potential energy curves almost coincide with the accurate CCSD(T)/CBS curves.

Research on C—C Bond Length Distribution in Hydrocarbon Molecules

The C--C bond dissociation energy （BDE） is a very important data in research of hydrocarbon cracking reactions, because it reflects the difficulty level of chemical reactions. But it is very difficult to obtain the C--C bond dissociation energy （BDE） by experiments, so using quantum chemistry calculation such as density functional theory （DFT） to study the C--C bond dissociation energy is a very useful means. The impact of acceptor substituents and donor substituents on the C--C bond length distribution was studied.

Hydrogen-bonding Interaction of 1,2,3-triazine-waters Complexes

Density functional theory B3LYP method with 6-31＋＋G＊＊ basis was used to optimize the geometries of the ground states for 1,2,3-triazine-（H2O）n（n=1,2,3） complexes. All calculations indicate that the 1,2,3- triazine-water complexes in the ground states have strong hydrogen-bonding interaction, and the complex having a N… .H-O hydrogen bond and a chain of water molecules which is terminated by a O. … .H-C hydrogen bond is the most stable. The H-O stretching modes of complexes are red-shifted relative to that of the monomer. In addition, the Natural bond orbit （NBO） analysis indicates that the intermolecular charge transfer between 1,2,3-triazine and water is 0.0222e, 0.0261e and 0.0273e for the most stable 1：1, 1：2 and 1：3 complexes, respectively. The first singlet （n, π＊） vertical excitation energy of the monomer 1,2,3-triazine and the hydrogen-bonding complexes of 1,2,3-triazine-（H2O）n were investigated by time-dependent density functional theory.

Identity-Based Encryption with Keyword Search from Lattice Assumption

Public key encryption scheme with keyword search （PEKS） enables us to search the encrypted data in a cloud server with a keyword, and no one can obtain any infor- mation about the encrypted data without the trapdoor corresponding to the keyword. The PEKS is useful to keep the management of large data storages secure such as those in a cloud. In this paper, to protect against quantum computer attacks, we present a lattice-based identity-based encryption scheme with key- word search. We have proved that our scheme can achieve ciphertext indistinguishability in the random oracle model, and our scheme can also achieve trapdoor security. In particular, our scheme can designate a unique tester to test and return the search results, therefore it does not need a secure channel. To the best of our knowledge, our scheme is the first iden- tity-based encryption scheme with keyword search from lattice assumption.

Certificateless Public Key Encryption with Keyword Search

Public Key Encryption with Keyword Search （PEKS）, an indispensable part of searchable encryption, is stock-in- trade for both protecting data and providing operability of encrypted data. So far most of PEKS schemes have been established on Identity-Based Cryptography （IBC） with key escrow problem inherently. Such problem severely restricts the promotion of IBC-based Public Key Infrastructure including PEKS component. Hence, Certificateless Public Key Cryptography （CLPKC） is efficient to remove such problem. CLPKC is introduced into PEKS, and a general model of Certificateless PEKS （CLPEKS） is formalized. In addition, a practical CLPEKS scheme is constructed with security and efficiency analyses. The proposal is secure channel free, and semantically secure against adaptive chosen keyword attack and keyword guessing attack. To illustrate the superiority, massive experiments are conducted on Enron Email dataset which is famous in information retrieval field. Compared with existed constructions, CLPEKS improves the efficiency in theory and removes the key escrow problem.

Density function theory study on the interaction between camptothecin and cytosine

Density function M06 method has been used to optimize the geometries of camptothecin-cytosine at 6-3 I＋G＊ basis. Finally, thirteen stabilized complexes have been obtained. Theories of atoms in molecules （AIM） and natural bond orbital （NBO） have been utilized to investigate the hydrogen bonds involved in all the complexes. The interaction energies of all the complexes are corrected by basis set superposition error （BSSE）. By the analysis of complexes interaction energy, charge density, second- order interaction energies E（2）; it is indicated that the complex 6 is the most stable structure.

Proposal of an Amide-Directed Carbocupration Mechanism for Copper-Catalyzed meta-Selective C-H Arylation of Acetanilides by Diaryliodonium Salts

We examined the puzzling mechanism for Cu-catalyzed meta-C-H arylation reaction of anilides by diaryliodonium salts through systematic theoretical analysis. The previously proposed anti-oxy-cupration mechanism featuring anti-1,2- or anti-1,4-addition of cuprate and oxygen to the phenyl ring generating a meta-cuprated intermediate was excluded due to the large activation barriers. Alternatively, a new amide-directed carbocupration mechanism was proposed which involves a critical rate- and regio-determining step of amide-directed addition of the Cu（III）-aryl bond across the phenyl C2=C3 double bond to form an orthocuprated, meta-arylated intermediate. This mechanism is kinetically the most favored among several possible mechanisms such as ortho-or para-cupration/migration mechanism, direct meta C-H bond cleavage mediated by Cu（III） or Cu（I）, and Cu（III）-catalyzed ortho-directed C-H bond activation mechanism this mechanism has been shown to Furthermore, the predicted regioselectivity based on favor the meta-arylation that is consistent with the experimental observations.

Theoretical Study of Hydrogen-Bond Interactions of CO_(2) in Organic Absorbent 1,3-Diphenylguanidine

Carbon capture and storage technology have been rapidly developed to reduce the carbon dioxide(CO2)emission into the environment.It has been found that the amine-based organic molecules could absorb CO_(2) efficiently and form the bicarbonate salts through hydrogen-bond(H-bond)interactions.Recently,the aqueous 1,3-diphenylguanidine(DPG)solution was developed to trap and convert CO_(2) to valuable chemicals under ambient conditions.However,how the DPG molecules interact with CO_(2) in an aqueous solution remains unclear.In this work,we perform molecular dynamics simulations to explore the atomistic details of CO_(2) in the aqueous DPG.The simulated results reveal that the protonated DPGH+and the bicarbonate anions prefer to form complexes through different H-bond patterns.These double H-bonds are quite stable in thermodynamics,as indicated from the accurate density functional theory calculations.This study is helpful to understand the catalytic mechanism of CO_(2) conversion in the aqueous DPG.