Photoelectron spectroscopy of 1-nitropropane and 1-nitrobutane anions

We present low-energy velocity map photoelectron imaging results for bare and Ar-solvated 1-nitropropane and 1-nitrobutane anions. We report the adiabatic electron affinity of 1-nitropropane as (223 ± 6) meV and that of 1-nitrobutane as (240 ± 6 meV). The vertical detachment energies of these two species are found to be (0.92 ± 0.05) and (0.88 ± 0.05) eV, respectively. The photoelectron spectra are discussed in the framework of Franck-Condon simulations based on density functional theory. We observe unusual resonances in the photoelectron spectra of both ions under study, whose kinetic energy is independent of the photon energy of the detaching radiation. We discuss possible origins of these resonances as rescattering phenomena, consistent with the experimental photoelectron angular distributions.     

Photoelectron imaging study of the effect of monohydration on O2 - photodetachment

The photodetachment of the O(2)(-).H(2)O cluster anion at 780 and 390 nm is investigated in comparison with O(2)(-) using photoelectron imaging spectroscopy. Despite the pronounced shift in the photoelectron spectra, the monohydration has little effect on the photoelectron angular distributions: for a given wavelength and electron kinetic energy (eKE) range, the O(2)(-).H(2)O angular distributions are quantitatively similar to those for bare O(2)(-). This observation confirms that the excess electron in O(2)(-).H(2)O retains the overall character of the 2ppi(g) HOMO of O(2)(-). The presence of H(2)O does not affect significantly the partial wave composition of the photodetached electrons at a given eKE. An exception is observed for slow electrons, where O(2)(-).H(2)O exhibits a faster rise in the photodetachment signal with increasing eKE, as compared to O(2)(-). The possible causes of this anomaly are (i) the long-range charge-dipole interaction between the departing electron and the neutral O(2).H(2)O skeleton affecting the slow-electron dynamics; and (ii) the s wave contributions to the photodetachment, which are dipole-forbidden for pi(g)(-1) transitions in O(2)(-), but formally allowed in O(2)(-).H(2)O due to lower symmetry of the cluster anion and the corresponding HOMO.     

I(-)·(CH3I)2 photoexcitation: the influence of dipole bound states on detachment and fragmentation

We present the results of a photoelectron imaging study of the I(-)·(CH(3)I)(2) cluster anion over excitation wavelengths 355-260 nm. The resulting spectra and photoelectron angular distributions (PADs) suggest extensive electron-molecule interaction following photoexcitation. Fragmentation channels are observed subsequent to excitation between 355 and 330 nm. The origin of these features, which begin 200 meV and peak 70 meV below the X band direct detachment threshold, is described in terms of a predissociative dipole bound state. The nature of the fragments detected and the energetics of the channel opening argue strongly in favor of an asymmetric, head to tail cluster anion geometry posited by Dessent et al. [Acc. Chem. Res. 31, 527 (1998)]. Above the direct detachment threshold, PADs display evidence of phenomena akin to electron-molecule scattering. The fragment anions disappear above the X band threshold but reappear some distance below the second (A) direct detachment band. At these energies there is also rapid variation of the X band PAD, an observation attributed to autodetachment via spin-orbit relaxation of the iodine core of the cluster.     

Solvent resonance effect on the anisotropy of NO(-)(N(2)O)(n) cluster anion photodetachment

Photodetachment from NO(-)(N(2)O)(n) cluster anions (n< or =7) is investigated using photoelectron imaging at 786, 532, and 355 nm. Compared to unsolvated NO(-), the photoelectron anisotropy with respect to the laser polarization direction diminishes drastically in the presence of the N(2)O solvent, especially in the 355 nm data. In contrast, a less significant anisotropy loss is observed for NO(-)(H(2)O)(n). The effect is attributed to photoelectron scattering on the solvent, which in the N(2)O case is mediated by the (2)Pi anionic resonance. No anionic resonances exist for H(2)O in the applicable photoelectron energy range, in line with the observed difference between the photoelectron images obtained with the two solvents. The momentum-transfer cross section, rather than the total scattering cross section, is argued to be an appropriate physical parameter predicting the solvent effects on the photoelectron angular distributions in these cluster anions.     

Depth and angular profiles of inelastic low-energy electron scattering in condensed molecular samples

Angular distributions of electrons scattered elastically and inelastically from cold solid molecular films of ethylene and nitrogen in various proportions, grown from the gas phase at different temperatures, have been studied by high-resolution electron energy loss spectroscopy. The probing depth of dipole and impact scattering has been investigated by covering the sample by overlayers of argon of increasing thickness. The angular distribution measured for elastically and inelastically dipole-scattered electrons was found to be peaked about the specular direction for all surface conditions studied, while a diffuse angular distribution was possible for electrons that underwent dipole-forbidden scattering. These results allow us to identify favorable conditions for monitoring the composition of a solid sample during the course of reactions occurring under exposure to low-energy electrons.     

Solvation effects on angular distributions in H- (NH3)n and NH2(-) (NH3)n photodetachment: role of solute electronic structure

We report 355 and 532 nm photoelectron imaging results for H(-)(NH(3))(n) and NH(2)(-)(NH(3))(n), n = 0-5. The photoelectron spectra are consistent with the electrostatic picture of a charged solute (H(-) or NH(2)(-)) solvated by n ammonia molecules. For a given number of solvent molecules, the NH(2)(-) core anion is stabilized more strongly than H(-), yet the photoelectron angular distributions for solvated H(-) deviate more strongly from the unsolvated limit than those for solvated NH(2)(-). Hence, we conclude that solvation effects on photoelectron angular distributions are dependent on the electronic structure of the anion, i.e., the type of the initial orbital of the photodetached electron, rather than merely the strength of solvation interactions. We also find evidence of photofragmentation and autodetachment of NH(2)(-)(NH(3))(2-5), as well as autodetachment of H(-)(NH(3))(5), upon 532 nm excitation of these species.     

Scattering of O2 from AL111

Experimental results are presented for the scattering of well-defined beams of molecular oxygen incident on clean Al(111). The data consist of scattered angular distributions measured as a function of incident angle, and for fixed incident angle, the dependence on surface temperature of the angular distributions. The measurements are interpreted in terms of a scattering theory that treats the exchange of energy between the translational and rotational motions of the molecule and the phonons of the surface using classical dynamics. The dependence of the measured angular distributions on incident beam angle and temperature is well explained by the theory. Rotational excitation and quantum excitation of the O(2) internal stretching mode are briefly discussed.     

Electron scattering by methanol and ethanol: a joint theoretical-experimental investigation

We present a joint theoretical-experimental study on electron scattering by methanol (CH(3)OH) and ethanol (C(2)H(5)OH) in a wide energy range. Experimental differential, integral and momentum-transfer cross sections for elastic electron scattering by ethanol are reported in the 100-1000 eV energy range. The experimental angular distributions of the energy-selected electrons are measured and converted to absolute cross sections using the relative flow technique. Moreover, elastic, total, and total absorption cross sections for both alcohols are calculated in the 1-500 eV energy range. A complex optical potential is used to represent the dynamics of the electron-alcohol interaction, whereas the scattering equations are solved iteratively using the Pade?'s approximant technique. Our calculated data agree well with those obtained using the Schwinger multichannel method at energies up to 20 eV. Discrepancies at high energies indicate the importance of absorption effects, included in our calculations. In general, the comparison between our theoretical and experimental results, as well as with other experimental data available in the literature, also show good agreement. Nevertheless, the discrepancy between the theoretical and experimental total cross sections at low incident energies suggests that the experimental cross sections measured using the transmission technique for polar targets should be reviewed.     

A Valence Photoelectron Imaging Investigation of Chiral Asymmetry in the Photoionization of Fenchone and Camphor

Photoelectron circular dichroism (PECD) is investigated in the valence ionization of selected fenchone enantiomers using a photoelectron imaging technique and circularly polarized synchrotron radiation. Theoretical modelling of the results using electron scattering calculations demonstrates that the observed chiral asymmetry in the photoelectron angular distributions depends strongly upon the final state scattering, and upon the quality of the molecular potential used for these calculations. However, very pronounced dependence on the orbital from which ionization occurs is also observed. Comparison with analogous results previously obtained for camphor reveals striking differences in the PECD, even when the ionizing orbitals are themselves left substantially unaffected by the changes in methyl groups’ substitution site. PECD measurements readily differentiate these molecules despite their very similar photoelectron spectra, demonstrating PECD to be a structurally sensitive probe.     

强阿秒XUV激走脉冲下H2^＋分子光电子能谱角分布非对称性

利用2D平面模型,求解了描述定向H2^＋分子和阿秒XUV脉冲相互作用的薛定谔方程,并求得光电子的角度分布．在计算模型中,采用基态1sσg和第一激发态2pσu的等比例混合态作为初始态,而激光脉冲的光子能量大于电离势,强度为10^14 W/cm^2． 计算结果表明,光电子角分布的非对称性和脉冲的宽度密切相关．这种非对称性实际上是由于初始态的基态和激发态的相干振荡而导致的．当使用长脉冲时,这种相干振荡的周期效应就会被平均而消失,从而产生的光电子能谱会呈对称角分布．     

Evaluation of elastic‐scattering cross sections for electrons and positrons over a wide energy range

Quantification of surface‐ and bulk‐analytical methods, e.g. Auger‐electron spectroscopy (AES), X‐ray photoelectron spectroscopy (XPS), electron‐probe microanalysis (EPMA), and analytical electron microscopy (AEM), requires knowledge of reliable elastic‐scattering cross sections for describing electron transport in solids. Cross sections for elastic scattering of electrons and positrons by atoms, ions, and molecules can be calculated with the recently developed code ELSEPA (Elastic Scattering of Electrons and Positrons by Atoms) for kinetic energies of the projectile from 10 eV to 50 eV. These calculations can be made after appropriate selection of the basic input parameters: electron‐density distribution, a model for the nuclear‐charge distribution, and a model for the electron‐exchange potential (the latter option applies only to scattering of electrons). Additionally, the correlation‐polarization potential and an imaginary absorption potential can be considered in the calculations. We report comparisons of calculated differential elastic‐scattering cross sections (DCSs) for silicon and gold at selected energies (500 eV, 5 keV, 30 keV) relevant to AES, XPS, EPMA, and AEM, and at 100 MeV as a limiting case. The DCSs for electrons and positrons differ considerably, particularly for medium‐ and high‐atomic‐number elements and for kinetic energies below about 5 keV. The DCSs for positrons are always monotonically decreasing functions of the scattering angle, while the DCSs for electrons have a diffraction‐like structure with several minima and maxima. A significant influence of the electron‐exchange correction is observed at 500 eV. The correlation‐polarization correction is significant for small scattering angles at 500 eV, while the absorption correction is important at energies below about 10 keV. Copyright © 2005 John Wiley & Sons, Ltd.     

Complete determination of the photoionization dynamics of a polyatomic molecule. II. Determination of radial dipole matrix elements and phases from experimental photoelectron angular distributions from A1Au acetylene

We present a fit to photoelectron angular distributions (PADs) measured following the photoionization of rotationally selected A1Au state acetylene. In the case of the 4(1)2Sigmau- vibronic state of the ion, we are able to use this fit to make a complete determination of the radial dipole matrix elements and phases connecting the prepared level to each photoelectron partial wave. We have also investigated other Renner-Teller subbands with a view to disentangling geometrical and dynamical contributions to the resulting PADs.     

Frequency modulated spectroscopy as a probe of molecular collision dynamics

We describe the application of frequency modulated spectroscopy (FMS) with an external cavity tuneable diode laser to the study of the scalar and vector properties of inelastic collisions. CN X(2)Sigma(+) radicals are produced by polarized photodissociation of ICN at 266 nm, with a sharp velocity and rotational angular momentum distribution. The collisional evolution of the distribution is observed via sub-Doppler FMS on the A(2)Pi-X(2)Sigma(+) (2,0) band. He, Ar, N(2), O(2) and CO(2) were studied as collider gases. Doppler profiles were acquired in different experimental geometries of photolysis and probe laser propagation and polarization, and on different spectroscopic branches. These were combined to give composite Doppler profiles from which the speed distributions and specific speed-dependent vector correlations could be determined. The angular scattering dynamics with species other than He are found to be very similar, dominated by backward scattering which accompanies transfer of energy between rotation and translation. The kinematics of collisions with He are not conducive to the determination of differential scattering and angular momentum polarization correlations. Angular momentum correlations show interesting differences between reactive and non-reactive colliders. We propose that this reflects differences in the potential energy surfaces, in particular, the nature and depth of attractive potential wells.     

Low-energy electron distributions from the photoionization of liquid water: a sensitive test of electron mean free paths

The availability of accurate mean free paths for slow electrons (<50 eV) in water is central to the understanding of many electron-driven processes in aqueous solutions, but their determination poses major challenges to experiment and theory alike. Here, we describe a joint experimental and theoretical study demonstrating a novel approach for testing, and, in the future, refining such mean free paths. We report the development of Monte-Carlo electron-trajectory simulations including elastic and inelastic electron scattering, as well as energy loss and secondary-electron production to predict complete photoelectron spectra of liquid water. These simulations are compared to a new set of photoelectron spectra of a liquid-water microjet recorded over a broad range of photon energies in the extreme ultraviolet (20–57 eV). Several previously published sets of scattering parameters are investigated, providing direct and intuitive insights on how they influence the shape of the low-energy electron spectra. A pronounced sensitivity to the escape barrier is also demonstrated. These simulations considerably advance our understanding of the origin of the prominent low-energy electron distributions in photoelectron spectra of liquid water and clarify the influence of scattering parameters and the escape barrier on their shape. They moreover describe the reshaping and displacement of low-energy photoelectron bands caused by vibrationally inelastic scattering. Our work provides a quantitative basis for the interpretation of the complete photoelectron spectra of liquids and opens the path to fully predictive simulations of low-energy scattering in liquid water.

Our study reveals the detailed influence of elastic and inelastic mean-free paths on the complete photoelectron spectra of liquid water, including the low-energy electron distributions and the reshaping of the primary photoelectron bands.     

Anisotropic hot electron emission from fullerenes

Photoelectron spectra for fullerenes C(60) and C(70) ionized using 800 nm laser pulses with pulse durations from 120 to 1000 fs show thermal electron kinetic energy distributions but they also exhibit angular anisotropy with respect to the laser light polarization. The effective temperature of electrons, measured along the laser polarization direction, is significantly higher than in the perpendicular direction. We explain this observation by considering that the emission of the thermal electrons is uncorrelated with the phase of the laser pulse, unlike directly ionized electrons, and, depending on the time of emission, they may experience an additional "kick" from the vector potential of the laser field when they are emitted from the molecule.     

Effects of solvation and core switching on the photoelectron angular distributions from (CO2)n(-) and (CO2)(n)(-).H2O

Photoelectron images are recorded in the photodetachment of two series of cluster anions, (CO(2))(n)(-), n=4-9 and (CO(2))(n)(-).H(2)O, n=2-7, with linearly polarized 400 nm light. The energetics of the observed photodetachment bands compare well with previous studies, showing evidence for switching between two anionic core structures: The CO(2)(-) monomer and covalent (CO(2))(2)(-) dimer anions. The systematic study of photoelectron angular distributions (PADs) sheds light on the electronic structure of the different core anions and indicates that solvation by several CO(2) molecules and/or one water molecule has only moderate effect on the excess-electron orbitals. The observed PAD character is reconciled with the symmetry properties of the parent molecular orbitals. The most intriguing result concerns the PADs showing remarkable similarities between the monomer and dimer anion cluster-core types. This observation is explained by treating the highest-occupied molecular orbital of the covalent dimer anion as a linear combination of two spatially separated monomeric orbitals.     

The dynamics of reaction of Cl atoms with tetramethylsilane

Rotational state distributions and state-selected CM-frame angular distributions were measured for HCl (v' = 0, j') products from the reaction of Cl-atoms with tetramethylsilane (TMS) under single collision conditions at a collision energy, E(coll), of 8.2 +/- 2.0 kcal mol(-1). The internal excitation of these products was very low with only 2% of the total energy available partitioned into HCl rotation. A transition state with a quasi-linear C-H-Cl moiety structure was computed and used to explain this finding. A backward peaking differential cross section was also reported together with a product translational energy (T') distribution with a maximum at T' approximately E(coll). This scattering behaviour is accounted for by reactions proceeding through a tight transition state on a highly skewed potential energy surface, which favours collisions at low impact parameters with a strong kinematic constraint on the internal excitation of the products. The large Arrhenius pre-exponential factor previously reported for this reaction is reconciled with the tight differential scattering observed in our study by considering the large size of the TMS molecule.     

Imaging ultrafast dynamics of molecules with laser-induced electron diffraction

We introduce a laser-induced electron diffraction method (LIED) for imaging ultrafast dynamics of small molecules with femtosecond mid-infrared lasers. When molecules are placed in an intense laser field, both low- and high-energy photoelectrons are generated. According to quantitative rescattering (QRS) theory, high-energy electrons are produced by a rescattering process where electrons born at the early phase of the laser pulse are driven back to rescatter with the parent ion. From the high-energy electron momentum spectra, field-free elastic electron-ion scattering differential cross sections (DCS), or diffraction images, can be extracted. With mid-infrared lasers as the driving pulses, it is further shown that the DCS can be used to extract atomic positions in a molecule with sub-angstrom spatial resolution, in close analogy to the standard electron diffraction method. Since infrared lasers with pulse duration of a few to several tens of femtoseconds are already available, LIED can be used for imaging dynamics of molecules with sub-angstrom spatial and a few-femtosecond temporal resolution. The first experiment with LIED has shown that the bond length of oxygen molecules shortens by 0.1 ? in five femtoseconds after single ionization. The principle behind LIED and its future outlook as a tool for dynamic imaging of molecules are presented.     

Dissociative electron attachment resonances in ammonia: a velocity slice imaging based study

Negative ion resonance states of ammonia are accessed upon capture of electrons with energy 5.5 eV and 10.5 eV, respectively. These resonance states dissociate to produce H(-) and NH(2)(-) fragment anions via different fragmentation channels. Using the velocity slice imaging technique, we measured the angular and kinetic energy distribution of the fragment H(-) and NH(2)(-) anions with full 0-2π angular coverage across the two resonances. The scattered H(-) ions at both resonances show variation in their angular distribution as a function of the kinetic energy indicating geometric rearrangement of NH(3)(-*) ion due to internal excitations and differ from the equilibrium geometry of the neutral molecule. The second resonance at 10.5 eV shows strong forward-backward asymmetry in the scattering of H(-) and NH(2)(-) fragment ions. Based on the angular distributions of the H(-) ions, the symmetry of the resonances at 5.5 eV and 10 .5 eV are determined to be A(1) and E, respectively, within C(3v) geometry.     

Effect of rotational energy on the reaction Li + HF(upsilon = 0,j)-->LiF + H: an experimental and computational study

In a crossed molecular-beam study we have measured angular and time-of-flight distributions of the product LiF from the reaction Li + HF(upsilon = 0)-->LiF + H at various collision energies ranging from 97 to 363 meV for three markedly different rotational state distributions of HF obtained at nozzle temperatures close to 315, 510, and 850 K. Particularly, for the low and intermediate collision energies we observe significant effects of the varying j-state populations on the shape of the product angular distributions. At 315 K an additional feature appears in the angular distributions which is interpreted as being due to scattering from HF dimers. The experimental data are compared with simulations of the monomer reaction based on extensive quasiclassical trajectory calculations on a new state-of-the-art ab initio potential energy surface. We find an overall good agreement between the theoretical simulations and the experimental data for the title reaction, especially at the highest HF nozzle temperature.