乙醛光解动力学的离子速度成像

利用时间切片离子速度成像技术在275～321 nm能量范围内重新研究了乙醛自由基通道CH₃+HCO的光解动力学. 通过共振增强多光子电离的方法探测甲基碎片. 对甲基的伞形振动基态和激发态(v₂=0和1)进行了影像探测. 乙醛通过T₁电子态系间窜越到S₁电子态的解离产物具有很高的动能释放和很低的内能激发,碎片的振动能和转动能随激发能量的增加而增加. 乙醛T₁电子态的势垒高度经测量高于基电子态3.881±0.006 eV.     

Formic acid desorption from graphitized Ni(110)

The adsorption/desorption behavior of formic acid from a monolayer of graphite carbon on Ni(110) was studied using AES, LEED and flash desorption spectroscopy. Formic acid adsorbed at 165 K did not form multilayers of adsorbate. Instead, due to strong hydrogen-bonding interactions the formic acid formed a two-dimensional condensed phase on the surface and exhibited zero-order desorption kinetics initially for a 30-fold change in initial coverage. The zero-order desorption rate constant was k_d = 10¹⁸ exp[?68.2 kJ mol^?1/RT]s^?1, suggesting a desorption transition state with nearly full translational and rotational freedom on the surface. The desorption kinetics and the coverage limit were consistent with the formation of a surface polymer-monomer equilibrium.     

振动和转动激发对N2在Fe(111)表面解离吸附的影响

N₂的解离化学吸附是工业合成氨的速控步骤. 基于最近构建的六维势能面,本文研究了N₂的初始振动激发和转动激发在Fe(111)表面的反应性的作用. 由于该反应具有重要的量子效应,通过六维量子动力学计算研究了入射能量低于1.6 eV 时振动激发的效应. 并采用准经典轨线计算揭示了高入射能量下的振动和转动激发的影响. 通过这些研究发现增加平动能量在一定程度上能提高解离几率,振动激发或转动激发能更有效地促进解离. 这项研究为重原子分子-表面反应的模式特异性动力学提供了有价值的见解.     

UV laser desorption of nitric oxide from semiconducting C<Subscript>60</Subscript>/Cu(111)

The desorption of NO from a well-characterized, epitaxially grown semiconducting C₆₀ surface is reported. Two different channels are identified in the laser desorption. Both channels yield a comparably high desorption cross section of σ₁=7.0×10^-17 cm² and σ₂=5.5×10^-17 cm² for the first and second channel, respectively. The laser desorbed NO molecules are detected with rovibrational state selectivity by (1+1) REMPI in the -bands. In the first channel the desorbing molecules are highly excited with an average kinetic energy of 〈E_kin〉=174 meV. The rotational population distribution can be fitted by a rotational temperature of T_rot=800 K. A rotational–translational coupling is observed, with velocities ranging from 1000 m/s for low to 1300 m/s for high rotational states. The vibrationally excited population is estimated to be less than 1% of the ground state. The second channel yields less excited molecules and an almost Boltzmann distributed rotational population with a temperature of T_rot=280 K. The apparent velocity distribution derived from the pump-probe delay yields molecules much too slow to be explained by even a thermal desorption. This desorption is probably caused by a long-lived electronic excitation in the substrate for which a lifetime of τ≈160 μs is estimated. PACS 42.62.Fi; 34.50.Dy; 68.49.Df; 68.43.Tj; 79.20.La     

The methane ν1(a1) vibrational state rotational structure obtained from high-resolution CARS-spectra of the Q-branch

The gaseous methane ν₁(a₁), Q-branch coherent anti-Stokes Raman scattering (CARS) spectra have been investigated at a resolution of 0.002 cm^?1. A complex rotational structure of the resolved Q-branch has been experimentally observed. This structure can be ascribed to strong tetrahedral splitting of the rotational levels of the upper vibrational state, which possibly occurs due to Fermi resonance between the ν₁(a₁) and 2ν₂(a₁) vibrational energy levels which are close to each other. An assignment of the observed spectral lines has been made, yielding the rotational constants B, D, and D_t for the ν₁(a₁) vibrational state of the methane molecule. The absolute Raman frequency ν₁ of the purely vibrational transition has been found.     

Isotope effects in the kinetics of simultaneous H and D thermal desorption from Pd

The kinetics of simultaneous hydrogen and deuterium thermal desorption from PdH_xD_y has been investigated. A novel experimental approach for the study of the transition state (TS) characteristics of the surface recombination reaction is proposed based on the analysis of the H and D partitioning into H₂, HD and D₂ molecules. It has been found that the hydrogen molecular isotopes distribution is determined by the energy differences of the corresponding TS of the atom-atom recombination reactions. On the other hand, the mechanisms and activation energies of the desorption process have been obtained. At 420 K, the desorption reaction changes from a surface recombination limiting mechanism during desorption from β-PdH_xD_y to a reaction limited by the rate of β to α phase transformation during the two phase coexistence. Surface recombination reaction becomes again rate limiting above 480 K, due to a change in the catalytic properties of the Pd surface. TS energies obtained from the kinetic analysis of the thermal desorption spectra are in good accordance with those obtained from the analysis of the H₂, HD and D₂ distributions. Anomalous TS energies have been observed for the H-D recombination reaction, which may be related to the heteronuclear character of this molecule.     

Laser desorption of NO from a thick C60 film

The desorption of NO molecules from a thick C₆₀ film is reported. A thermal desorption spectrum indicates two adsorption sites with binding energies of E_b = 0.30 eV and 0.55 eV. For laser desorption the fullerene surface is exposed to NO and excited by 7 ns UV laser pulses. Desorbing NO molecules are recorded state selectively as well as time resolved. The time-of-flight measurement indicates three different desorption pathways. A fast channel shows rovibronic temperatures of T_rot(v″ = 0) = 370 K, T_rot(v″ = 1) = 390 K and T_vib = 610 K as well as strong rotational-translational coupling. The desorption yield for the fast channel increases linearly with pulse energy with a desorption cross section of σ = (5.1 ± 0.9) × 10⁻¹⁷ cm². Dominating the signal for small J″ values is a slow channel with low rotational and translational temperatures of about 110 K. We assign this peak to a laser-induced thermal desorption. For large pump-probe delays the data deviate from the Maxwellian flux distribution and a third channel appears with extremely late arrival times.     

The microwave spectrum and molecular conformation of peroxynitric acid (HOONO2)

The rotational spectrum of peroxynitric acid has been investigated in the 40- to 120-GHz region. The spectrum of the ground state is complicated by tunneling of the OH group, which causes a doubling of the asymmetric rotor spectrum. The magnitude of the tunneling splitting is such that it causes Coriolis interactions between the energy levels of the two tunneling states which lead to perturbations in the rotational spectrum. A combined analysis of the a- and b-type pure rotational transitions with the c-type tunneling transitions allows a perturbation-free determination of the rotational constants for the ground state. A similar analysis of the low-lying NO₂ torsional vibration at 145(6) cm⁻¹ has also been carried out. The dipole moments for each state have been determined by analysis of the second-order Stark effect. The molecular structure analysis indicates that all the heavy atoms are planar and only the hydrogen atom is out of the heavy atom plane. The preferred orientation of the hydrogen atom with respect to the plane of the heavy atoms is at an angle ∼106° with respect to the cis conformation.     

Effects of surface corrugation on the molecular rotational dependence of H2 dissociative adsorption dynamics on Cu(100)

We investigate and discuss how surface corrugation affects the molecular rotational dependence of H₂ dissociative adsorption dynamics on Cu(100) by performing six-dimensional (6D) quantum dynamics calculations. We calculate the dissociative adsorption probability as a function of the initial rotational state J and the normal energy E_norm of incident molecules, and compare with the dissociative adsorption results obtained by four-dimensional (4D) quantum dynamics calculations where the surface is treated as flat. In our calculation, for the case of normal incidence, the increase in dissociative adsorption probability with increasing E_norm and the non-monotonic behavior of dissociative adsorption probability with respect to J are suppressed on a corrugated surface as compared to that on a flat surface.     

Rovibrational state distribution of deuterium molecules resulting from D-atom interaction with Ni(110)

Using the REMPI technique we have studied the internal state distribution of deuterium molecules produced by the interaction of atomic deuterium with chemisorbed deuterium on Ni(110) at 180 K. We observed molecules in vibrational states up to v = 3 with a mean vibrational energy of 220 meV. The mean rotational energies of the molecules in the vibrational states v = 0 to 3 are 185 meV, 133 meV, 75 meV and 37 meV, respectively. The overall mean rotational energy amounts to 150 meV, again far in excess of the mean rotational energy of molecules accommodated to the surface. The data are consistent with direct interactions of the impinging particles with the adsorbed particles (Eley-Rideal reaction and collision induced desorption), for which it is assumed that a considerable amount of the potential and kinetic energy of the impinging atoms is channeled into translational and internal energy of the reaction products.     

225∽260 nm波段溴化氰光解动力学系统性研究

本文报道了在自行搭建的时间切片离子速度成像装置上进行的225∽260 nm波段内溴化氰光解动力学的研究. 在该波段内选取了若干溴原子(²P_3/2或²P_1/2)的共振线对产物溴原子的共振电离并采集其切片影像,得到了光解产物的总平动能谱,进而获得了产物氰基的振转态布居等信息. 本文发现了在Br^*通道,产物氰基的内能激发比Br通道低;Br和Br^*通道产物氰基振动的最高布居分别为v=0和1. 另外,还发现对于Br通道,溴化氰分子在长波处与短波处解离时,氰基产物的振转激发差异很大,这揭示了其显著不同的光解动力学.     

Dynamical studies and product analysis of O(1D) + H2/D2 reactions

The aim of this study was to analyse the dynamics of O(¹D)?+?H₂/D₂ reactions using quasiclassical trajectory calculations on a double-valued potential energy surface for H₂O. Produced on the photodissociation of stratospheric ozone, the excited oxygen atom is a highly reactive species whose chemistry plays a key role in the ozone depletion cycle. In order to make comparisons with experiment, we studied these reactions at fixed translational collision energies. In particular, we consider the reactive cross sections, the thermal rate constants, the opacity function, and the differential cross sections. In addition, we also study the energy distribution of the products and compare the results with experiment and calculations based on phase space statistical theory. Results for the rotational population of the OH products are also compared with experimental results. The agreement between our results and experiment reinforces the accuracy of the H₂O potential energy surface used.     

Photodissociation of iodocyclohexane at 266 and 277 nm: Energy partitioning and curve crossing analysis

The photodissociation dynamics of iodocyclohexane (C₆H₁₁I) at 266 and 277 nm has been investigated by ion velocity imaging technique. The velocity distributions, angular distributions and relative quantum yields are obtained for I (²P_3/2) (denoted I) and I (²P_1/2) (denoted I*) fragments. The energy partitioning shows that about 70% of the available energy goes into the internal excitation of the photofragments for both dissociation channels. From the angular distributions, we found the value of the anisotropy parameter β for I* at the corresponding excitation wavelength was less than that for I. Based on the measured angular distributions and relative quantum yields, the relative fractions of each excited state to the products are determined. The curve crossing probabilities between the ³Q₀ and ¹Q₁ states are determined 0.503 at 266 nm and 0.443 at 277 nm.     

Laser spectroscopy of desorbing molecules

In this article the application of tunable dye lasers to desorption phenomena is illuminated. These lasers provide radiation continuously tunable from 105 nm in the vacuum ultraviolet to about 10 m in the mid-IR. By employing either laser induced fluorescence (LIF) or resonance enhanced multiphoton ionization (REMPI) spectroscopy almost all diatomic and many polyatomic molecules can be probed with the sensitivity required to detect desorbing molecules under UHV conditions. The spectral resolution of the lasers is sufficiently high that rotational state selectivity is achieved. Recent developments permit in addition the velocity distributions of molecules to be determined with internal quantum state resolution. Therefore very detailed information about the molecular dynamics has been obtained. In most experiments so far reactive recombinations off surfaces have been investigated. In this paper special emphasis will be given to the recombination of hydrogen on copper and palladium surfaces. For these systems very detailed data about the internal state populations at various surface temperatures have been obtained. The rotational cooling previously observed in molecular beam scattering has also been established for desorption. Strong vibrational excitation has been observed, which in the case of desorption from copper may be associated with the recombination dynamics, whereas for desorption of D₂ from Pd(100) a molecular precursor state might be responsible. By measuring the velocity distribution in each quantum state, the complete energetics of the desorbing molecules has been determined. Some first experiments on laser induced desorption with state selective detection of the desorbing molecules will also be discussed. Finally, making use of the polarization analysis of the signal, alignment effects in the desorption can be observed, permitting observation of molecular dynamics with a magnifying glass.Heisenberg fellow of the Deutsche Forschungsgemeinschaft     

The accommodation of the translational and rotational energy of a gas in a Knudsen flow past a thin wire

The paper presents the results obtained in determining the accommodation coefficients for the translational and rotational energy of gas molecules in a Knudsen flow past a thin wire. The method used was based on numerically solving the complete heat balance equation for a wire probe. The accommodation coefficients were determined for H₂, N₂, CH₄, and CO₂ on a gilded tungsten surface. For hydrogen with a quenched rotational energy, a negative accommodation coefficient of rotational energy was obtained due to the conversion of the rotational energy of incident molecules into the translational energy of reflected molecules.     

Desorption dynamics in N2O decomposition on Pd(110)

The decomposition of N₂O was studied on Pd(110) through analysis of the angular and velocity distributions of desorbing products by means of angle-resolved thermal desorption combined with time-of-flight techniques. Both desorption and decomposition of N₂O(a) were completed below 170 K, simultaneously emitting N₂. N₂ showed two desorption peaks, β₁-N₂ at 152 K and β₂-N₂ at 134–140 K. The former revealed an inclined emission at ±43° off the normal in a plane along the (001) direction and a hyper-thermal translational energy, whereas the latter showed a cosine angular distribution without an excess translational energy. Different desorption channels were proposed to yield these desorption.     

Features of the structure and dynamics of Me1−x (NH4) x SCN (Me = K, Rb) mixed crystals

Neutron scattering is used to study the structure and dynamics of Me_{1 − x} (NH₄) _x SCN (Me = K, Rb) mixed crystals along the concentration section of 0.0 < x < 1.0 at room temperature 10 and 290 K. Phase transitions in Me_{1 − x} (NH₄) _x SCN mixed crystals are analyzed by neutron powder diffraction. The measured spectra of inelastic incoherent neutron scattering from mixed crystals in a concentration range of 0.0 < x < 1.0 at 10 are transformed into the generalized phonon density of states G(E) in the one-phonon incoherent approximation. Using G(E), we determine the changes in ammonium ion dynamics during phase transitions. Low energy resonance and local translational (two bands) and librational (two bands) modes are observed in the disordered rhombic phase at 10 K. The low energy resonance mode is not found in the ordered monoclinic phase at 10 K, though the local translational mode in the form of two bands and the local librational mode in the form of four bands are present there. The low energy resonance mode appears due to hybridization of the phonon spectrum of the host crystal with rotational tunneling modes of the split librational ground state of the impurity’s molecular ammonium ion.     

Monomer counterrotations and tunneling splitting in CO dimer by data of millimeter wave spectroscopy

Analysis of the rotational spectrum of the molecular dimer (CO)₂ measured in the millimeter wave range has been performed and four new rotational states are revealed. Three of these states are characterized by almost free rotations of both monomers in the dimer. These states have approximately the same first term σ in the expansion of the rotational energy in powers of the rotational angular momentum J for various values of the momentum projections on the dimer axis (K=0, 1, 2) and various rotational constants B. The intrinsic rotational angular momenta of CO dimers, j₁=j₂=1, are determined from the σ value. In addition, a state with K=2 is found which corresponds to one of the known shape isomers of (CO)₂. The values of the tunneling splitting for each of the new states are determined. The results indicate that previous data on the suppressed tunneling are determined by the asymmetry of internal rotations in the CO monomers rather than by the _K value.     

Rovibrational excitation within the infinite conical well: Desorption of diatomic molecules

An analytic model for the hindered rotational states of a diatomic molecule adsorbed upright on a solid surface is discussed. Various model dynamics situations, within the sudden approximation, designed to simulate desorption are presented and rotational state distributions are calculated including both rotational and translational degrees of freedom. Criteria are established for observing rotationally cool desorbed molecules.     

Product state distributions and rotational polarization for the crossed beam reactions of Ca with F2 and NF3

Product state distributions of the CaF products from the thermal crossed beam reactions Ca + F₂ and Ca + NF₃ have been measured using laser induced fluorescence (LIF) techniques. We obtain information about the rotational and vibrational distributions by generating synthetic band profiles and comparing them with those observed. The inverted vibrational distributions indicate direct reaction mechanisms. For Ca + F₂ the fractionf′ of energy is nearly half going into product translation and the remainder being devided nearly equally between product rotation and vibration. For Ca + NF₃ the largest fraction of the available reaction exoergicity goes into vibrational excitation of the newly formed CaF products. In addition, we have probed the rotational polarization of CaF product molecules. This gives direct information on the role of angular momentum alignment in reactive scattering.