Single-field slice-imaging with a movable repeller: photodissociation of N2O from a hot nozzle.

We present a new photo-fragment imaging spectrometer, which employs a movable repeller in a single field imaging geometry. This innovation offers two principal advantages. First, the optimal fields for velocity mapping can easily be achieved even using a large molecular beam diameter (5 mm); the velocity resolution (better than 1%) is sufficient to easily resolve photo-electron recoil in (2 + 1) resonant enhanced multiphoton ionization of N2 photoproducts from N2O or from molecular beam cooled N2. Second, rapid changes between spatial imaging, velocity mapping, and slice imaging are straightforward. We demonstrate this technique's utility in a re-investigation of the photodissociation of N2O. Using a hot nozzle, we observe slice images that strongly depend on nozzle temperature. Our data indicate that in our hot nozzle expansion, only pure bending vibrations--(0, v2, 0)--are populated, as vibrational excitation in pure stretching or bend-stretch combination modes are quenched via collisional near-resonant V-V energy transfer to the nearly degenerate bending states. We derive vibrationally state resolved absolute absorption cross-sections for (0, v2 ≤ 7, 0). These results agree well with previous work at lower values of v2, both experimental and theoretical. The dissociation energy of N2O with respect to the O((1)D) + N2¹Σ(g)⁺ asymptote was determined to be 3.65 ± 0.02 eV.

Inverse velocity dependence of vibrationally promoted electron emission from a metal surface.

All previous experimental and theoretical studies of molecular interactions at metal surfaces show that electronically nonadiabatic influences increase with molecular velocity. We report the observation of a nonadiabatic electronic effect that follows the opposite trend: The probability of electron emission from a low-work function surface--Au(111) capped by half a monolayer of Cs--increases as the velocity of the incident NO molecule decreases during collisions with highly vibrationally excited NO(X(2)pi((1/2)), V = 18; V is the vibrational quantum number of NO), reaching 0.1 at the lowest velocity studied. We show that these results are consistent with a vibrational autodetachment mechanism, whereby electron emission is possible only beyond a certain critical distance from the surface. This outcome implies that important energy-dissipation pathways involving nonadiabatic electronic excitations and, furthermore, not captured by present theoretical methods may influence reaction rates at surfaces.

The work function of submonolayer cesium-covered gold: a photoelectron spectroscopy study.

Using visible and x-ray photoelectron spectroscopy, we measured the work function of a Au(111) surface at a well-defined submonolayer coverage of Cs. For a Cs coverage producing a photoemission maximum with a He-Ne laser, the work function is 1.61+/-0.08 eV, consistent with previous assumptions used to analyze vibrationally promoted electron emission. A discussion of possible Cs layer structures is also presented.

Observation of a change of vibrational excitation mechanism with surface temperature: HCl collisions with Au(111).

We have measured the vibrational excitation probability (Pv) of HCl incident on a Au(111) surface at kinetic energies (Ei) of 0.59 eV to 1.37 eV and surface temperatures (Ts) of 273 K to 1073 K. For all energies, the slope of the Pv as a function of Ts exhibits a sharp increase above Ts approximately 800 K. We show this change in slope and the threshold behavior of Pv to be consistent with a change in excitation mechanism from an electronically adiabatic mechanical mechanism to an electronically nonadiabatic mechanism involving excited electron-hole pairs.

Photofragment translation spectroscopy of ClN3 at 248 nm: determination of the primary and secondary dissociation pathways.

Photofragmentation translational spectroscopy was used to identify the primary and secondary reaction pathways in the KrF laser (248 nm) photodissociation of chlorine azide (ClN(3)) under collision-free conditions. Both the molecular channel producing NCl (X (3)Sigma,a (1)Delta) + N(2) and the radical channel producing Cl ((2)P(J)) + N(3) were analyzed in detail. Consistent with previously reported velocity map ion imaging experiments [N. Hansen and A. M. Wodtke, J. Phys. Chem. A 107, 10608 (2003)] a bimodal translational energy distribution is seen when Cl atoms are monitored at mz = 35(Cl(+)). Momentum-matched N(3) counterfragments can be seen at mz = 42(N(3) (+)). The characteristics of the observed radical-channel data reflect the formation of linear azide radical and another high-energy form of N(3) (HEF-N(3)) that exhibits many of the characteristics one would expect from cyclic N(3). HEF-N(3) can be directly detected by electron-impact ionization more than 100 mus after its formation. Products of the unimolecular dissociation of HEF-N(3) are observed in the mz = 14(N(+)) and mz = 28(N(2) (+)) data. Anisotropy parameters were determined for the primary channels to be beta = -0.3 for the NCl forming channel and beta = 1.7 and beta = 0.4 for the linear N(3) and HEF-N(3) forming channels, respectively. There is additional evidence for secondary photodissociation of N(3) and of NCl.

Bridging the cluster-to-bulk divide: electron attachment time-of-flight mass spectrometry reveals geometrical shell closings in (SF6) (n) clusters (n = 2 - 550).

We report electron attachment time-of-flight mass spectra of SF (6) clusters over a wide range of cluster sizes, revealing a simple pattern of geometrical shell closings which persists from large clusters (n approximately 500) to as small as perhaps n = 14. Quantitative structural properties of these nanocrystallites are derived. These observations, made possible by an extraordinarily gentle ionization method and mass spectral analysis, suggest that bulk crystalline packing may be important for much smaller molecular clusters than previously observed, confirming theoretical predictions.

The dynamics of "stretched molecules": experimental studies of highly vibrationally excited molecules with stimulated emission pumping.

We review stimulated emission pumping as used to study molecular dynamics. The review presents unimolecular as well as scattering studies. Topics include intramolecular vibrational redistribution, unimolecular isomerization and dissociation, van der Waals clusters, rotational energy transfer, vibrational energy transfer, gas-surface interactions, atmospheric effects resulting from nonequilibrium vibrational excitation, and vibrational promotion of electron transfer.

Laser desorption electron attachment time-of-flight mass spectrometry: a new approach to detection of involatile compounds.

We report initial results of a new method for obtaining mass spectra of involatile compounds: laser desorption electron attachment time-of-flight mass spectrometry. With this approach, laser desorbed neutral molecules are entrained in a molecular beam and subsequently ionized by low energy electron attachment. Mass analysis is carried out by a linear time-of-flight. We present a description of the apparatus and a number of examples of our early results on: van der Waals condensates of SF6, Fullerenes, derivatized Fullerenes, perfluorinated polyethers, polyphenylethers, and 5-bromouracil.

Vibrational promotion of electron transfer.

By using laser methods to prepare specific quantum states of gas-phase nitric oxide molecules, we examined the role of vibrational motion in electron transfer to a molecule from a metal surface free from the complicating influence of solvation effects. The signature of the electron transfer process is a highly efficient multiquantum vibrational relaxation event, where the nitrogen oxide loses hundreds of kilojoules per mole of energy on a subpicosecond time scale. These results cannot be explained simply on the basis of Franck-Condon factors. The large-amplitude vibrational motion associated with molecules in high vibrational states strongly modulates the energetic driving force of the electron transfer reaction. These results show the importance of molecular vibration in promoting electron transfer reactions, a class of chemistry important to molecular electronics devices, solar energy conversion, and many biological processes.

The "Ozone Deficit" Problem: O2(X, v ge 26) + O(3P) from 226-nm Ozone Photodissociation.

Highly vibrationally excited O(2)(X(3)sigmag(-), v >/= 26) has been observed from the photodissociation of ozone (O(3)), and the quantum yield for this reaction has been determined for excitation at 226 nanometers. This observation may help to address the "ozone deficit" problem, or why the previously predicted stratospheric O(3) concentration is less than that observed. Recent kinetic studies have suggested that O(2)(X(3)sigmag(-), v >/= 26) can react rapidly with O(2) to form O(3) + O and have led to speculation that, if produced in the photodissociation of O(3), this species might be involved in resolving the discrepancy. The sequence O(3) + hv --> O(2)(X(3)sigmag(-), v >/= 26) + O; O(2)(X(3)sigmag(-), v >/= 26) + O(2) --> O(3) + O (where hv is a photon) would be an autocatalytic mechanism for production of odd oxygen. A two-dimensional atmospheric model has been used to evaluate the importance of this new mechanism. The new mechanism can completely account for the tropical O(3) deficit at an altitude of 43 kilometers, but it does not completely account for the deficit at higher altitudes. The mechanism also provides for isotopic fractionation and may contribute to an explanation for the anomalously high concentration of heavy O(3) in the stratosphere.

High-sensitivity detection of NO in a flame using a tunable ArF laser.

A tunable, narrow-band ArF laser has been used for laser-induced fluorescence detection of NO in natural abundance in a flame experiment. P and R branches of the D(2)Sigmaupsilon' = 0?X(2)Pi(3/2,1/2)upsilon'' transition were observed probing rotational states between J'' = 19.5 and J'' = 44.5. A single-shot detection limit of 1 part in 10(6) was found with a monochromator-based, dispersed-fluorescence detection system. In an experimental setup, determination of undispersed laser-induced fluorescence detection limits at or below the 1-part-in-10(9) range should be possible, because the narrow-band laser can be used to suppress all other sources of contaminating fluorescence even for detection of trace NO. The NO B(2)Piupsilon' = 7 ? X(2)Piupsilon'' = 0 transition was also observed in a cell experiment but not in the flame and is reported here.