UV laser photofragment GaCH3 detected by far UV laser mass spectrometry

The GaCH₃ radical has been directly detected by far UV laser mass spectrometry for the first time, as a UV laser photofragment from gaseous trimethylgallium Ga(CH₃)₃, but not from triethylgallium, Ga(C₂H₅)₃. The relative yield Y() of GaCH₃ was measured, at various UV photolysis laser wavelengths =193, 210 and 245 nm, and follows the absorption spectrum of the Ga(CH₃)₃ precursor molecules.     

Ultrasound irradiation promotes the synthesis of new 1,2,4-triazolo[1,5-a]pyrimidine

Ultrasonic irradiation was used in the synthesis of a series of novel 1,2,4-triazolo[1,5-a]pyrimidines. The products were synthetized from the cyclocondensation reaction of 1,1,1-trifluoro-4-metoxy-3-alken-2-one [CF₃C(O)CHC(R)OMe, where R = Ph, 4-F-C₆H₄, 4-Br-C₆H₄, 4-I-C₆H₄, 4-CH₃-C₆H₄, 4-CH₃O-C₆H₄, Thien-2-yl, Biphen-4-yl] or β-enaminones [RC(O)CHCHNMe₂, where R = Ph, 4-F-C₆H_4, 4-Br-C₆H_4, 4-I-C₆H_4, 4-CH₃-C₆H₄, 4-CH₃O-C₆H₄, 4-NO₂-C₆H₄, Thien-2-yl, Biphen-4-yl, Naphth-2-yl, Pyrrol-2-yl, CCl₃] with 5-amino-1,2,4-triazole in acetic acid at 99 °C with 5–17 min of ultrasound irradiation. This methodology has shown several advantages, such as shorter reaction times, mild conditions, high regioselectivity, and excellent yields, when compared with conventional thermal heating (oil bath).     

三甲基镓在Pd(111)表面吸附解离及表面预吸附H和O的影响

利用X-射线光电子能谱（XPS）和程序升温脱附谱（TPD）研究了三甲基镓在Pd（111）表面的吸附和解离行为,并考察了表面预吸附H和O的影响。结果表明,在吸附温度为140 K时,三甲基镓在Pd（111）上主要为解离吸附,此时表面物种为Ga（CH₃）_x （x=1,2,3）和CH_x物种。加热将导致Ga的甲基化合物中的Ga-C键发生分步断裂,在不同温度下产生CH₄和H₂从表面脱附。同时,XPS结果证实了在275~325 K的温度区间内存在Ga甲基化合物的分子脱附。退火至更高温度,表面只观察到积碳和金属Ga物种,这二者随着温度的继续升高逐渐向体相扩散。在Pd（111）表面预吸附O和H对上述吸附和解离行为存在显著的影响。当表面预吸附H时,脱附产物CH₄和H₂的脱附主要位于315 K,可归属为一甲基镓的解离脱附。当表面预吸附O时,只在258 K观察到CH₄和H₂的脱附峰,可能来自于Pd-O-Ga（CH₃）₂吸附结构的解离.     

Surface reactions of 2-iodopropane on GaAs(1 0 0)

The surface reactions of 2-iodopropane ((CH₃)₂CHI) on gallium-rich GaAs(1 0 0)-(4 × 1), was studied by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). CH₃CHICH₃ adsorbs molecularly at 120 K but dissociates below room temperature to form chemisorbed 2-propyl ((CH₃)₂CH) and iodide (I) species. Thermal activation causes desorption of the molecular species at 240 K, and this occurs in competition with the further reactions of the (CH₃)₂CH and I chemisorbed species. Self-coupling of the (CH₃)₂CH results in the formation of 2,3-dimethylbutane ((CH₃)₂CH-CH(CH₃)₂) at 290 K. β-Hydride elimination in (CH₃)₂CH yields gaseous propene (CH₃CHCH₂) at 550 K while reductive elimination reactions of (CH₃)₂CH with surface hydrogen yields propane (CH₃CH₂CH₃) at 560 K. Recombinative desorption of the adsorbed hydrogen as H₂ also occurs at 560 K. We observe that the activation barrier to carbon-carbon bond formation with 2-propyls on GaAs(1 0 0) is much lower than that in our previous investigations involving ethyl and 1,1,1-trifluoroethyl species where the β-elimination process was more facile. The difference in the surface chemistry in the case of 2-propyl species is attributable to its rigid structure resulting from the bonding to the surface via the second carbon atom, which causes the methyl groups to be further away from the surface than in the case of linear ethyl and 1,1,1-trifluoroethyl species. The β-hydride and reductive elimination processes in the adsorbed 2-propyl species thus occurs at higher temperatures, and a consequence of this is that GaI desorption, which is expected to occur in the temperature range 550-560 K becomes suppressed, and the chemisorbed iodine leaves the surface as atomic iodine.     

A non‐enzymatic model based on an acyl transfer reaction for the formation of energy‐rich acetyl phosphate in organic solvents and in a biphasic system

The formation of acetyl phosphate (AcP), an energy‐rich phosphate compound, was studied through the reaction of 2,4‐dinitrophenyl acetate with H₂PO solubilized with Kryptofix® 222 or as a tetra‐n‐butylammonium ((n‐C₄H₉)₄N⁺) salt in organic media. The results indicated that the rate of the reaction in acetonitrile is strongly inhibited by the addition of water, suggesting that the water added to the medium preferentially solvates the H₂PO anion, inhibiting its action as a nucleophile and allowing it to act as a general base catalyst, which leads to the hydrolysis of the ester. The utilization of various organic solvents in the acetyl transfer process demonstrated that the specific interaction of the solvent with water accelerates the process, by desolvation of H₂PO, which can act as a nucleophile. Finally, a formation/transformation cycle of AcP was studied in a biphasic system (water/CH₂Cl₂) using Kryptofix® 222 and (n‐C₄H₉)₄N⁺BF as both the carrier and solubilizing agent for KH₂PO₄. Copyright © 2010 John Wiley & Sons, Ltd.     

Exact distribution of cluster size and perimeter for two-dimensional percolation

Exact series expansion data of Sykes et al. are used to calculate the average numberc _n and perimeters _n of clusters of sizen20 in the site percolation problem for the triangular, square, and honeycomb lattice. At the percolation thresholdp _n we find a sharply peaked distribution of perimeterss _n with mean s _n =((1–p _n )/p _c )n+O(n ) and width s _n ² –S _n ²n ^1.6 where1/=0.39. This perimeter s _n should not be interpreted as a cluster surface in the usual sense. Two tests confirm the universality hypothesis with reasonable accuracy. The asymptotic decay of the cluster numbersc _n withn is consistent with the postulated asymmetry aboutp _c : logc _n –n forn with1 forp<p _c and1/2 forp>p _c .     

Benzene thermal synthesis and characterization of crystalline carbon nitride

A new solvothermal route has been successfully used to prepare crystalline carbon nitride powder from 1,3,5-trichlorotriazine (C₃N₃Cl₃) and lithium nitride (Li₃N) in benzene at 360 °C and 6–7 MPa. The as-prepared sample was brown and was analyzed by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). The results show that the powder mainly consists of -C₃N₄, -C₃N₄ and some unidentified carbon-nitrogen crystalline phases. The experimental lattice constants of -C₃N₄ (a=6.48 Å,c=4.72 Å) and -C₃N₄ (a=6.43 Å,c=2.47 Å) match the latest ab-initio calculations (a=6.47 Å and c=4.72 Å for -C₃N₄, a=6.40 Å and c=2.40 Å for -C₃N₄) quite well. The relative nitrogen-to-carbon composition ratio is 0.76. Only C–N and C=N bonds were demonstrated by XPS and FTIR. The feasibility of this synthetic method is discussed and this approach may provide a possible and very effective way to realize the growth of pure crystalline carbon nitride materials, which is quite different from the conventional solid-state reactions (SSR). PACS 81.10.-h; 81.10.Dn; 81.05.Zx; 61.66.Fn; 42.70.Nq     

Adsorption and thermal reaction of short-chain alkanethiols on GaAs(1 0 0)

By means of temperature-programmed desorption (TPD) and X-ray photoemission spectroscopy (XPS) with synchrotron radiation, we investigated the adsorption and thermal decomposition of alkanethiols (RSH, R = CH₃, C₂H₅, and C₄H₉) on a GaAs(1 0 0) surface. All chemisorbed alkanethiols can deprotonate to form thiolates below 300 K via dissociation of the sulfhydryl hydrogen (-SH). Two types of thiolates species are observed on GaAs(1 0 0), according to adsorption on surface Ga and As sites. The thiolates adsorbed on a Ga site preferentially recombine with surface hydrogen to desorb as a molecular thiol at 350-385 K. The thiolate on the As site exhibits greater thermal stability and undergoes mainly dissociation of the C-S bond at ∼520 K, independent of the alkyl chain length. The decomposition of CH₃S either directly desorbs CH₃ or transfers the CH₃ moiety onto the surface. The surface CH₃ further evolves directly from the surface at 665 K. The dissociations of C₂H₅S and C₄H₉S yield surface C₂H₅ and C₄H₉, which further decompose to desorb C₂H₄ and C₄H₈, respectively, via β-hydride elimination. The complete decomposition of alkanethiol leads to the formation of surface S without deposition of carbon. Adsorption of CH₃SSCH₃ results in the formation of surface CH₃S at initial exposures via scission of the S−S bond. Compared with the adsorption of CH₃SH, the CH₃S on the Ga site exhibits greater thermal stability because surface hydrogen is absent. At a high exposure, CH₃SSCH₃ can absorb molecularly on the surface and decompose to desorb CH₃SCH₃ via formation of a CH₃SS intermediate.     

An experimental and theoretical kinetic study of t-butyl radical reaction with molecular oxygen

In this work, a unifying picture of the kinetics of the t-C₄H₉ + O₂ reaction is presented by combining the current and previous experimental results with theory. Direct, time-resolved experiments were performed over a wide temperature range (200–500 K) at low pressures (0.3–6 Torr) using a photoionization mass spectrometry method. The kinetic measurements of the t-butyl + O₂ reaction were initiated by laser photolysis of pinacolone at 193 nm or t-butyl bromide at 248 nm to produce t-C₄H₉ radicals. Energies calculated by quantum chemistry at the CCSD(T)/CBS and CASPT2/CBS levels of theory were used in master equation simulations of the kinetics of the t-C₄H₉ + O₂ reaction. The calculations successfully reproduce the pressure and temperature dependencies of both the current low-pressure experiments and literature kinetic data at about atmospheric pressure as well as the literature kinetic data for the overwhelmingly most important bimolecular reaction channel, t-C₄H₉ + O₂ → i-C₄H₈ + HO₂ in the intermediate temperature range. The experimentally constrained master equation model was utilized to simulate the t-C₄H₉ + O₂ reaction kinetics over wide range of conditions. The results of these simulations are provided in ChemKin compatible PLOG format for later use.     

离子速度成像系统校准及1,4-氯溴丁烷的紫外光解动力学

大气臭氧层破坏越来越严重, 卤代烷烃在太阳紫外线辐射下解离生成破坏臭氧的游离态卤素原子, 是主要元凶之一. 本文选用碘甲烷作为校准分子, 利用离子速度成像技术和共振增强多光子电离技术测得碘甲烷在266 nm紫外光解离下产生的基态碘原子I(²P_3/2)在不同聚焦电压下的离子速度影像, 得到离子速度成像系统的放大系数N=1.13. 并利用该系统研究了1, 4-氯溴丁烷在～ 234 nm紫外辐射下的解离动力学, 分析讨论了解离产生的基态Br (²P_3/2)和激发态Br^* (²P_1/2)的速度和角度分布信息, 揭示了1, 4-氯溴丁烷在～ 234 nm紫外光解离产生基态Br原子和激发态Br^* 原子的通道都是源于C-Br键排斥势能面上的快速解离. 文中通过计算碎片影像角度分布的各项异性参数β值, 得到了生成基态Br(²P_3/2)和激发态Br^* (²P_1/2) 两个解离通道中的平行跃迁和垂直跃迁比例. 另外, 本文还对氯溴甲烷, 1, 2-氯溴乙烷, 1, 3-氯溴丙烷和1, 4-氯溴丁烷在～ 234 nm下的光解动力学进行比较, 分析得到双卤代烷烃分子解离机理对烷基支链长度的依赖关系.     

Scanning tunneling microscopy study of molecular order at liquid-solid interfaces

Adsorbates of normal alkane C₃₆H₇₄, cycloalkanes (CH₂)₄₈ and (CH₂)₇₂, decanol C₁₀H₂₁OH, 4-hexyl-4-CyanoBiphenyl (6CB) and 4-octyl-4t-CyanoBiphenyl (8CB) on graphite and -Nb₃I₈ were studied by Scanning Tunneling Microscopy (STM), and the molecular arrangements at the liquid-solid interface were examined. Large-scale STM images show that the adsorbates possess complex multilayered structures, and that molecular ordering at the liquid-solid interfaces occurs primarily in the immediate vicinity of the substrate. Molecular-scale STM images are primarily determined by the electronic contributions of the most protruded atoms of the topmost overlayer. The underlying overlayers and the substrate affect the images indirectly by perturbing the topography of the topmost overlayer. The STM images of the adsorbates on graphite show that the atomically flat surface of graphite leads organic molecules to form lamella-like structures, while on the grooved surface of -Nb₃I₈, long chain-like molecules are trapped in the grooves. We were unable to image the cycloalkanes on -Nb₃I₈, which suggests that the cycloalkanes cannot assemble on the grooved surface due to a mismatch between the molecular shape and surface topography. The layers of 6CB and 8CB adsorbed on -Nb₃I₈ exhibit two types of domains, which may be related to how the grooves of the -Nb₃I₈ surface are occupied by the organic molecules. The STM images of decanol adsorbed on -Nb₃I₈ show two domains of different brightness. The relative brightness of these domains switches reversibly as the gap resistance is changed in the region around –60 M.     

Quasi-periodic solutions of nonlinear wave equations with quasi-periodic forcing

This work focuses on one-dimensional (1D) quasi-periodically forced nonlinear wave equations. This means studying with Dirichlet boundary conditions, where ε is a small positive parameter, (t) is a real analytic quasi-periodic function in t with frequency vector ω=(ω₁,ω₂…,ω_m) and the nonlinearity h is a real analytic odd function of the form It is shown that, under a suitable hypothesis on (t) and h, there are many quasi-periodic solutions for the above equation via KAM theory.     

Effects of ortho‐substituents in SE1 protonolysis of phenylmercuric chloride

The kinetics of the reactions of o‐substituted phenylmercuric chlorides, o‐RC₆H₄HgCl (R = CH₃, H, C₂H₅O, CH₃O, C₆H₅, F, COOC₂H₅, Cl, Br, CF₃, NO₂), with hydrochloric acid in 80% aqueous dioxane in the presence of NaI were studied. The reactions are of the first order. The rate constant at 40°C decreases in the order of R: CH₃ > H > C₂H₅O > CH₃O > C₆H₅ > F > COOC₂H₅ > Cl > Br > CF₃ > NO₂. The analysis of effects of those o‐substitutes is carried out through multiple regression of log k/k_H with the corresponding inductive substituent constants σ_I and the various resonance substituent constants σ, σ_R(BA), σ, σ and σ_x, and the corresponding Swain–Lupton field effect constant and resonance effect constant . The results showed that o‐substituent intramolecular coordination with the neighbor mercury (field effect) is the main effect in effects of o‐substituents on rate of the S_E1 protonolysis. Copyright © 2007 John Wiley & Sons, Ltd.     

Mössbauer spectroscopic studies of (n-C n H2n +1NH3)2SnX6 (n=0-4; X = Cl or Br) and their related complexes

Complexes of the type (n-C _n H_2n +1NH₃)₂SnX₆ (0n 4 and X=Cl or Br) have been investigated with a variety of physico-chemical techniques. The structural phase transitions were found in some of these complexes. The temperature dependence of the Mössbauer spectral absorption area for (C₂H₅NH₃)₂SnCl₆ and (C₂H₅NH₃)₂SnBr₆ changed sharply at phase transition temperatures. The temperature dependences for (n-C₄H₉NH₃)₂SnCl₆ and (n-C₄H₉NH₃)₂SnBr₆ decreased gradually with an increase in temperature. The correlation between the temperature dependence of the spectral absorption area and the motion of n-C _n H_2n+1NH₃ ⁺ ions is discussed.     

13C-NMR Study of Some Substituted 9-Acridanone Derivatives

¹³C-NMR spectra of several 9-acridanones with different substituents both on the ring (R₁ = CH₃, OCH₃, NH₂, N(CH₃)₂, NO₂) and at the nitrogen atom (R₂ = H, CH₃ C₂H₅, CH₂-C₆H₅, C[tbnd]C-CH₃, (CH₂)₂N(C₂H₂)₂, CH=C=CH₂) have been recorded. The C-NMR chemical shifts are discussed as a function of the nature of the substituent, the importance of peri steric interactions and the electronic structure of the acridanone ring. There is a good linear relationship between the total electronic density and the chemical shifts.     

Optic nonlinearities of a copper complex of pyrazinoporphyrazine

For the copper complex of pyrazinoporphyrazine AzaPhcCu(C(CH₃)₃)₈ in CH₂Cl₂, we use nanosecond pulses to measure its third-order nonlinear optic effects at 532 nm. The results show that its effective third-order nonlinear refractive index n ^eff ₂ (–7.85 × 10^–10 esu) is larger than that of the AzaPhcCu(C₁₂H₂₅)₄ and the CuPc(OC₅H₁₁)₈. The reverse saturable absorption (RSA) of AzaPhcCu-(C(CH₃)₃)₈ is demonstrated by the ratio of effective excited state to ground state absorption cross sections. The observed intersystem crossing lifetime _isc of AzaPhcCu(C(CH₃)₃)₈ (15 ns) and AzaPhcCu(C₁₂H₂₅)₄ (45 ns) are longer than that of CuPc(OC₅H₁₁)₈ (5.0 ns). The aza-substituents are suggested to form a S₁(n, ^*) state as their lowest excited singlet-states, and their radiationless intersystem crossing rates (1/_isc) are discussed with the spin-orbit coupling _S|H _SO|_T and the vibronic coupling _S|_T effects between S₁ and T₁ states.     

Invariant subspaces of clustering operators

A class of clustering operators is defined which is a generalization of a transfer matrix of a Gibbs lattice field with an exponential decay of correlations. It is proved that for small values of the clustering operator has invariant subspaces which are similar tok-particle subspaces of the Fock space. The restriction of the clustering operator onto these subspaces resembles the operator exp(-H _k, whereH _k is thek- particle Schrödinger Hamiltonian in nonrelativistic quantum mechanics. The spectrum of eachH _k,k1, is contained in the interval (C ₁^k,C ₂^k). These intervals do not intersect with each other.     

Crystal structures of 3‐methyl‐2(1H)‐quinoxalinone and three substituted derivatives

3‐Methyl‐2(1H)‐quinoxalinone and three derivatives (3,7‐dimethyl‐2(1H)‐quinoxalinone, 3‐methyl‐6,7‐dichloro‐2(1H)‐quinoxalinone and 3‐methyl‐7‐nitro‐2(1H)‐quinoxalinone) have been synthesised and analysed by ¹H NMR and IR spectral spectroscopies. The crystal structures have been determined at room temperature from X‐ray single crystal diffraction data for three of them and from powder diffraction data for the nitro derivative. 3‐Methyl‐2(1H)‐quinoxalinone crystallises in the P2₁/c monoclinic system, 3,7‐dimethyl‐2(1H)‐quinoxalinone in the Pbca orthorhombic system and the two others compounds in the P$\overline {1} $ triclinic system. For the nitro derivative, C? H$\cdots $ N short contacts are established between the carbon of the methyl and the double bounded nitrogen of the ring. For the three other compounds N? H$\cdots $ O hydrogen bonds involve the atoms of the heterocyclic ring. Copyright © 2011 John Wiley & Sons, Ltd.     

On the Spectrum of the Generator of an Infinite System of Interacting Diffusions

We study the spectrum of the operator

Mössbauer study of a novel binuclear Fe(II/III) delocalized-valence compound

In this paper, we briefly summarize the main conclusions of the Mössbauer analysis of [L₂Fe₂(-OH)₃] (ClO₄)₂·2CH₃OH·2H₂O with L=N,N',N"-trimethyl-1,4,7-triazacyclononane, a novel dimeric iron compound, which possesses a central exchange-coupled delocalized-valence Fe(II/III) unit. The complete delocalization of the excess electron in the dimeric iron center is concluded from the indistinguishability of the two iron sites in Mössbauer spectroscopy. The magnetic Mössbauer spectra imply a system spinS _t=9/2 for the dimer in its ground state. The values for hyperfine and spin-Hamiltonian parameters, obtained from simulations of the Mössbauer spectra, are =0.74 mms^–1, E _Q=–2.14 mms^–1,A =–10.6 T,A =–13.5 T andD=1.8 cm^–1. The system spinS _t=9/2 is interpreted to be a consequence of double-exchange coupling.