Signatures of H2CO photodissociation from two electronic states

Even in small molecules, the influence of electronic state on rotational and vibrational product energies is not well understood. Here, we use experiments and theory to address this issue in photodissociation of formaldehyde, H2CO, to the radical products H + HCO. These products result from dissociation from the singlet ground electronic state or the first excited triplet state (T1) of H2CO. Fluorescence spectra reveal a sudden decrease in the HCO rotational energy with increasing photolysis energy accompanied by substantial HCO vibrational excitation. Calculations of the rotational distribution using an ab initio potential energy surface for the T1 state are in very good agreement with experiment and strongly support dominance of the T1 state in the dynamics at the higher photolysis energies.     

First-principles theory for the H + H2O, D2O reactions

A full quantum dynamical study of the reactions of a hydrogen atom with water, on an accurate ab initio potential energy surface, is reported. The theoretical results are compared with available experimental data for the exchange and abstraction reactions in H + D2O and H + H2O. Clear agreement between theory and experiment is revealed for available thermal rate coefficients and the effects of vibrational excitation of the reactants. The excellent agreement between experiment and theory on integral cross sections for the exchange reaction is unprecedented beyond atom-diatom reactions. However, the experimental cross sections for abstraction are larger than the theoretical values by more than a factor of 10. Further experiments are required to resolve this.     

Observation of Feshbach resonances in the F + H2 --> HF + H reaction

Reaction resonances, or transiently stabilized transition-state structures, have proven highly challenging to capture experimentally. Here, we used the highly sensitive H atom Rydberg tagging time-of-flight method to conduct a crossed molecular beam scattering study of the F + H2 --> HF + H reaction with full quantum-state resolution. Pronounced forward-scattered HF products in the v' = 2 vibrational state were clearly observed at a collision energy of 0.52 kcal/mol; this was attributed to both the ground and the first excited Feshbach resonances trapped in the peculiar HF(v' = 3)-H' vibrationally adiabatic potential, with substantial enhancement by constructive interference between the two resonances.     

A Quantum State-Resolved Insertion Reaction: O((1)D) + H(2)(J = 0) --> OH((2) product operator product operator product operator, v, N) + H((2)S)

The O((1)D) + H(2) --> OH + H reaction, which proceeds mainly as an insertion reaction at a collisional energy of 1.3 kilocalories per mole, has been investigated with the high-resolution H atom Rydberg "tagging" time-of-flight technique and the quasiclassical trajectory (QCT) method. Quantum state-resolved differential cross sections were measured for this prototype reaction. Different rotationally-vibrationally excited OH products have markedly different angular distributions, whereas the total reaction products are roughly forward and backward symmetric. Theoretical results obtained from QCT calculations indicate that this reaction is dominated by the insertion mechanism, with a small contribution from the collinear abstraction mechanism through quantum tunneling.     

Experimental Studies and Theoretical Predictions for the H + D2 rarr > HD + D Reaction

The H + H(2) exchange reaction constitutes an excellent benchmark with which to test dynamical theories against experiments. The H + D(2) (vibrational quantum number v = 0, rotational quantum number j = 0) reaction has been studied in crossed molecular beams at a collision energy of 1.28 electron volts, with the use of the technique of Rydberg atom time-of-flight spectroscopy. The experimental resolution achieved permits the determination of fully rovibrational state-resolved differential cross sections. The high-resolution data allow a detailed assessment of the applicability and quality of quasi-classical trajectory (QCT) and quantum mechanical (QM) calculations. The experimental results are in excellent agreement with the QM results and in slightly worse agreement with the QCT results. This theoretical reproduction of the experimental data was achieved without explicit consideration of geometric phase effects.     

XF(X=H,D,T)的高精度理论研究

运用包括非迭代三激发电子相关耦合簇CCSD(T)方法和Dunning等人使用的相关一致aug-CC-PVxZ(x=D,T,Q,5)自洽基组对XF(X=H,D,T)分子进行了结构优化,优化值然后被插值到CBS极限.结果表明随着x的增大aug-CC-PVxZ系列基组优化的结构逼近实验值,计算频率与实验值最大差距不足1%,最小仅为0.099%,平衡间距最大只有0.8%的差距.通过计算还表明:在结构优化和频率分析时CCSD(T)显示出优秀的特性,但在研究与边界态或解离有关的问题时,CCSD(T)不能给出良好的结果,相反CCSD方法却能给出合理的解离极限.最后我们研究了XF(X=H,D,T)的分子势能函数和光谱常数,理论结果与已知实验值吻合的非常好.首次获得了XF(X=H,D,T)系列分子的ωeye,ωeze,β,γ,He,Fe值.     

Nonadiabatic interactions in the Cl + H2 reaction probed by ClH2- and ClD2- photoelectron imaging

The degree of electronic and nuclear coupling in the Cl + H2 reaction has become a vexing problem in chemical dynamics. We report slow electron velocity-map imaging (SEVI) spectra of ClH2- and ClD2-. These spectra probe the reactant valley of the neutral reaction potential energy surface, where nonadiabatic transitions responsible for reactivity of the Cl excited spin-orbit state with H2 would occur. The SEVI spectra reveal progressions in low-frequency Cl.H2 bending and stretching modes, and are compared to simulations with and without nonadiabatic couplings between the Cl spin-orbit states. Although nonadiabatic effects are small, their inclusion improves agreement with experiment. This comparison validates the theoretical treatment, especially of the nonadiabatic effects, in this critical region of the Cl + H2 reaction, and suggests strongly that these effects are minor.     

披碱草焦磷酸化酶基因EdHP1的功能分析

氢离子焦磷酸化酶(H~+-PPase)是一类H~+转运蛋白,它以焦磷酸(PPi)水解底物,水解PPi产生的自由能与H~+跨膜转运相藕联,将细胞质中的H~+泵入液泡中,建立跨液泡膜电化学梯度,形成质子驱动力,为无机离子及其他溶质进出液泡提供动力,有利于植物维持细胞离子平衡和渗透平衡,增强植物的抗逆性。基于前期对披碱草(Elymus dahuricus)H~+-PPase基因Ed HP1克隆的基础,对其表达谱及基因功能进行了进一步研究。结果表明,通过Northern blot分析发现,该基因在披碱草中受干旱、低温非生物胁迫诱导表达。通过对转Ed HP1基因烟草在干旱、低温环境下的功能分析发现,过表达Ed HP1基因可以提高转基因烟草对干旱、冷胁迫的抗性。     

The transition state of the f + h2 reaction

The transition state region of the F + H(2) reaction has been studied by photoelectron spectroscopy of FH(2)(-). New para and normal FH(2)(-)photoelectron spectra have been measured in refined experiments and are compared here with exact three-dimensional quantum reactive scattering simulations that use an accurate new ab initio potential energy surface for F + H(2). The detailed agreement that is obtained between this fully ab initio theory and experiment is unprecedented for the F + H(2) reaction and suggests that the transition state region of the F + H(2) potential energy surface has finally been understood quantitatively.     

Size-Specific Infrared Spectra of Benzene-(H2O)n Clusters (n = 1 through 7): Evidence for Noncyclic (H2O)n Structures

Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C(6)H(6)-(H(2)O)n clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C(6)H(6)-(H(2)O)n structure in which benzene is on the surface of a cyclic (H(2)O)n cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H(2)O)n clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H(2)O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H(2)O)n structures will occur.     

Theoretical and experimental rate constants for two isotopic modifications of the reaction h + h2

Theoretical rate constants for two isotopic modifications of the simplest possible chemical reaction, namely, H + D(2) --> HD + D and D + H(2) --> HD + H, are presented. Experimental results, which have previously been obtained in the higher temperature regime by a shock tube technique, are combined with lower temperature results to give an experimental determination of the rate behavior over the large temperature range approximately 200 to 2000 K. It is now possible to assess the accuracy of ab initio potential energy surface calculations and to judge theoretical chemical kinetic methods.     

Desorption of H from Si(111) by resonant excitation of the Si-H vibrational stretch mode

Past efforts to achieve selective bond scission by vibrational excitation have been thwarted by energy thermalization. Here we report resonant photodesorption of hydrogen from a Si(111) surface using tunable infrared radiation. The wavelength dependence of the desorption yield peaks at 0.26 electron volt: the energy of the Si-H vibrational stretch mode. The desorption yield is quadratic in the infrared intensity. A strong H/D isotope effect rules out thermal desorption mechanisms, and electronic effects are not applicable in this low-energy regime. A molecular mechanism accounting for the desorption event remains elusive.     

Seemingly anomalous angular distributions in H + D₂ reactive scattering

When a hydrogen (H) atom approaches a deuterium (D(2)) molecule, the minimum-energy path is for the three nuclei to line up. Consequently, nearly collinear collisions cause HD reaction products to be backscattered with low rotational excitation, whereas more glancing collisions yield sideways-scattered HD products with higher rotational excitation. Here we report that measured cross sections for the H + D(2) → HD(v' = 4, j') + D reaction at a collision energy of 1.97 electron volts contradict this behavior. The anomalous angular distributions match closely fully quantum mechanical calculations, and for the most part quasiclassical trajectory calculations. As the energy available in product recoil is reduced, a rotational barrier to reaction cuts off contributions from glancing collisions, causing high-j' HD products to become backward scattered.     

SF~n（n=-1,0,＋1）分子离子基态Murell-Sorbie势能函数的计算

基于Gaussian03软件包,利用密度泛函理论的B3P68方法,选用多种基组对SFn(n=-1,0,+1)分子离子基态进行几何优化和频率计算.优选出6-311g(3df),6-311++g(3df),D95++(3df)基组,进一步对SF分子和SF+,SF-分子离子基态进行单点能扫描计算.采用最小二乘法拟合得到SFn(n=-1,0,+1)分子离子基态的Murell-Sorbie势能函数.首次给出SFn(n=-1,0,+1)分子离子基态力常数(Re),完善了光谱参数(Be,αe,ωe,ωexe)的理论值,为SFn(n=-1,0,+1)分子离子基态的后期研究提供重要的参考.     

Chemical cartography: finding the keys to the kinetic labyrinth

Very high resolution lasers allow spectroscopic pictures to be taken following a collision between two molecular reactants. The features of these "pictures" are the electronic, vibrational, rotational, and translational motions of the atomic particles, which relate the quantum states of the reactants to the quantum states of the products. Such state-to-state kinetic information can be used to test the shape and nature of the interaction potential that controls the collision process. The potential itself is akin to a map of the terrain through mountains and valleys where elevation is a measure of energy instead of height. Accurate mapping of this potential surface leads to an understanding of the forces which control rates and mechanisms of chemical reactions. The application of four different advanced laser techniques to the study of collisions between "hot" hydrogen(H) atoms and carbon dioxide(CO(2)) molecules has provided a wealth of information about both reactive and nonreactive collisions for this system. The availability of data for rotationally, vibrationally, and translationally inelastic excitation of CO(2) by H atoms, when compared with data for reactive events producing OH + CO, provides insights into the dynamics of collisions between H and CO(2), and illustrates the future promise of these powerful techniques for elucidating features of potential energy surfaces.     

Infrared signature of structures associated with the H+(H2O)n (n = 6 to 27) clusters

We report the OH stretching vibrational spectra of size-selected H+(H2O)n clusters through the region of the pronounced "magic number" at n = 21 in the cluster distribution. Sharp features are observed in the spectra and assigned to excitation of the dangling OH groups throughout the size range 6 相似文献   

Dynamics of the reaction of methane with chlorine atom on an accurate potential energy surface

The reaction of the chlorine atom with methane has been the focus of numerous studies that aim to test, extend, and/or modify our understanding of mode-selective reactivity in polyatomic systems. To this point, theory has largely been unable to provide accurate results in comparison with experiments. Here, we report an accurate global potential energy surface for this reaction. Quasi-classical trajectory calculations using this surface achieve excellent agreement with experiment on the rotational distributions of the hydrogen chloride (HCl) product. For the Cl + CHD(3) → HCl + CD(3) reaction at low collision energies, we confirm the unexpected experimental finding that CH-stretch excitation is no more effective in activating this late-barrier reaction than is the translational energy, which is in contradiction to expectations based on results for many atom-diatom reactions.     

重组禽流感病毒H5+H7亚型三价灭活疫苗(H5 N1Re-11株、Re-12株+H7N9Re-2)对黄羽肉鸡免疫效果抗体监测试验

试验通过对重组禽流感病毒(H5+H7)三价灭活疫苗(H5N1Re-11株+Re-12株+H7N9 H7Re-2株)在慢速型黄羽肉鸡上接种后产生抗体效价值的情况,来评价重组禽流感病毒(H5+H7)三价灭活疫苗(H5N1Re-11株+Re-12株+H7N9 Re-2株)对黄羽肉鸡预防高致病性禽流感疫病的效果。结果表明黄羽肉鸡在15日龄接种重组禽流感病毒(H5+H7)三价灭活疫苗(H5N1Re-11株+Re-12株+H7N9 H7Re2株),45日龄进行二次免疫,75日龄进行三免,产生H5N1Re-11株抗体滴度、H5N1Re-12株抗体滴度、H7N9 Re-2株抗体滴度都较高,从抗体消长规律来看对慢速型黄羽肉鸡出栏前都有很好的保护力。试验在黄羽肉鸡上接种重组禽流感病毒(H5+H7)三价灭活疫苗(H5N1Re-11株+Re-12株+H7N9 H7Re2株)首次免疫后14 d产生抗体有保护力,二免后28日龄抗体滴度达到高峰,对慢速型黄羽肉鸡有很好的保护力。     

CH5+: the infrared spectrum observed

Protonated methane, CH5+, has unusual vibrational and rotational behavior because its three nonequivalent equilibrium structures have nearly identical energies and its five protons scramble freely. Although many theoretical papers have been published on the quantum mechanics of the system, a better understanding requires spectral data. A complex, high-resolution infrared spectrum of CH5+ corresponding to the C-H stretching band in the 3.4-micrometer region is reported. Although no detailed assignment of the individual lines was made, comparison with other carbocation spectra strongly suggests that the transitions are due to CH5+.     

Theoretical studies of the energetics and dynamics of chemical reactions

Computational studies of basic chemical processes not only provide numbers for comparison with experiment or for use in modeling complex chemical phenomena such as combustion, but also provide insight into the fundamental factors that govern molecular structure and change which cannot be obtained from experiment alone. We summarize the results of three case studies, on HCO, OH + H(2), and O + C(2)H(2), which illustrate the range of problems that can be addressed by using modern theoretical techniques. In all cases, the potential energy surfaces were characterized by using ab initio electronic structure methods. Collisions between molecules leading to reaction or energy transer were described with quantum dynamical methods (HCO), classical trajectory techniques (HCO and OH + H(2)), and statistical methods (HCO, OH + H(2), and O + C(2)H(2)). We can anticipate dramatic increases in the scope of this work as new generations of computers are introduced and as new chemistry software is developed to exploit these computers.