ALBERT

Notes: The vibrational relaxation dynamics of CO chemisorbed on small Pt and Rh particles supported on SiO2 has been investigated by picosecond time-resolved infrared transient bleaching experiments. A vibrational T1 lifetime of ≈7 ps has been observed for several different samples, independent of polarization, pump intensity, and sample temperature from 100–400 K. A 1:3 isotopic dilution has no effect upon T1. This T1 lifetime is a factor of 10–50 times shorter than T1 reported for metal carbonyl cluster compounds in solution and on SiO2 supports. Two possible mechanisms are considered to account for the rapid T1 decay; redistribution of the energy throughout the broad CO vibrational band, and relaxation directly to electron–hole pairs in the metal particles.

Notes: The A 3Π1←X 1Σ+ laser-induced fluorescence excitation spectrum of the NeIBr van der Waals complex is reported and analyzed to extract information regarding the structure and vibrational predissociation dynamics of the complex. While no definitive geometric information regarding NeIBr is obtained, our data indicate that a linear geometry is at least plausible. The vibrational predissociation lifetimes are a strong function of A state vibrational level and range from 2.6 to 23 ps. The variation in lifetime with vibrational level is consistent with the results of previous measurements on rare gas–halogen complexes, particularly NeBr2.

Notes: Infrared pump–probe characterization of the excited state lifetimes reveals that CO bound to isolated metal sites (T1=140±20 ps) persists longer than the signal observed for CO bound to (approximate)35 A(ring) diameter metal particles (≤18 ps), suggesting paticipation of electron–hole excitations in the larger metal particles.

Notes: Vibrational overtone photodissociation is used to examine the spectroscopy and vibrational predissociation lifetimes of HN3 in its ground electronic state. Direct overtone pumping of the N–H stretching levels 5νNH and 6νNH prepares molecules in selected states (v,J,K) near 15 100 and 17 700 cm−1 of vibrational energy; spin-forbidden NH(X 3 Σ−) dissociation fragments are detected by laser-induced fluorescence. Photodissociation spectra of beam-cooled HN3 display mixing of individual rotational levels of the nνNH vibrations with several background states, with derived coupling matrix elements in the range 0.01–0.1 cm−1. Vibrational predissociation lifetimes of mixed components of 5νNH are state specific, with variations of a factor of 2 for only 0.1 cm−1 energy differences. Average lifetimes for low J, K are 210 ns for 5νNH and 0.95 ns for 6νNH. The ratio of decay rates for the two overtone levels, k(6νNH)/k(5νNH)=220, is much greater than predicted by statistical theory, which gives a ratio of 4.

Notes: Picosecond and nanosecond lasers and pulsed molecular beam techniques have been used to measure the infrared photodissociation spectra, the product state distributions, and the predissociation lifetimes of vibrationally excited nitric oxide dimer (NO)2 . Results for the ν1 (v=1) symmetric NO stretching mode and the ν4 (v=1) antisymmetric NO stretching mode are presented. Predissociation lifetimes are determined by time-resolved laser induced fluorescence probing of the NO monomer product appearance rate. A dramatic mode dependence of the predissociation lifetimes is observed with the higher energy ν1 mode decaying in approximately 1 ns, and the lower energy ν4 mode decaying in approximately 40 ps. The mode dependence is independent of which product state is probed. The product state distributions show that 75% to 80% of the available energy is channeled into relative translational energy of the fragments for both modes. Rotational state distributions are Boltzmann-like with temperatures ranging from 71 to 112 K depending on both the initially excited mode and on the NO product spin–orbit state. Predissociation from ν1 produces NO fragments in the 2Π1/2 and 2 Π3/2 states with equal probability. Predissociation from ν4 exhibits a propensity for producing the lower energy 2 Π1/2 spin–orbit state. The observations are discussed in terms of various vibrational predissociation mechanisms, including vibrational potential coupling and electronically nonadiabatic predissociation.

Notes: The rotational-, spin-, and lambda doublet-state distributions for nitric oxide (NO) formed in the CO2 laser multiphoton dissociation of methyl nitrite, CH3ONO, in a pulsed molecular beam are reported. Upon methyl nitrite photolysis by temporal square wave infrared laser pulses at 983 cm−1 of 50 ns duration and 800 MW/cm2 intensity, the low-lying rotational levels of the nitric oxide fragments formed in the 2Π1/2 (F1) and 2Π3/2 (F2) spin-orbit states exhibited Boltzmann-like population distributions, characterizable by the rotational temperatures TR (F1)=400±10 K and TR (F2)=530±100 K; the integrated populations for J〈30.5 of the two spin components were in the ratio F1/F2=2.7 : 1. For those highly rotationally excited levels with J(approximately-greater-than)24.5 there is no measurable spin preference, the level population depending solely on total internal energy Eint. There is no apparent preference for formation of either lambda doublet component and there is no observable fragment alignment, the nascent NO species exhibiting an isotropic distribution of angular momentum vectors.

Notes: The electronic energy transfer pathways that occur following collisions between I2 in the E ion-pair electronic state (v=0, J=55) and He and Ar atoms have been determined. The nearby D, D′, and β ion-pair states are populated, but with relative branching ratios that vary with the rare gas collision partner. In He/I2 collisions, the D state is preferentially populated, while Ar/I2 collisions preferentially populate the β electronic state. Bimolecular rate constants and effective hard sphere collision cross sections have been determined for each channel; the cross sections range from 7.0±1.0 Å2 for populating the β state with Ar collisions to 0.9±0.2 Å2 for populating the D′ state with He collisions. For both rare gas collision partners, and all three final electronic states, low vibrational levels are populated, in rough accord with the relevant Franck–Condon factors. There is little propensity observed for population of vibrational levels that are in near resonance with the initially prepared level in the E state. © 2002 American Institute of Physics.

Notes: The mechanism of the reaction CH4+O(1D2)→CH3+OH was investigated by ultrafast, time-resolved and state-resolved experiments. In the ultrafast experiments, short ultraviolet pulses photolyzed ozone in the CH4⋅O3 van der Waals complex to produce O(1D2). The ensuing reaction with CH4 was monitored by measuring the appearance rate of OH(v=0,1;J,Ω,Λ) by laser-induced fluorescence, through the OH A←X transition, using short probe pulses. These spectrally broad pulses, centered between 307 and 316 nm, probe many different OH rovibrational states simultaneously. At each probe wavelength, both a fast and a slow rise time were evident in the fluorescence signal, and the ratio of the fast-to-slow signal varied with probe wavelength. The distribution of OH(v,J,Ω,Λ) states, Pobs(v,J,Ω,Λ), was determined by laser-induced fluorescence using a high-resolution, tunable dye laser. The Pobs(v,J,Ω,Λ) data and the time-resolved data were analyzed under the assumption that different formation times represent different reaction mechanisms and that each mechanism produces a characteristic rovibrational distribution. The state-resolved and the time-resolved data can be fit independently using a two-mechanism model: Pobs(v,J,Ω,Λ) can be decomposed into two components, and the appearance of OH can be fit by two exponential rise times. However, these independent analyses are not mutually consistent. The time-resolved and state-resolved data can be consistently fit using a three-mechanism model. The OH appearance signals, at all probe wavelengths, were fit with times τfast(approximate)0.2 ps, τinter(approximate)0.5 ps and τslow(approximate)5.4 ps. The slowest of these three is the rate for dissociation of a vibrationally excited methanol intermediate (CH3OH*) predicted by statistical theory after complete intramolecular energy redistribution following insertion of O(1D2) into CH4. The Pobs(v,J,Ω,Λ) was decomposed into three components, each with a linear surprisal, under the assumption that the mechanism producing OH at a statistical rate would be characterized by a statistical prior. Dissociation of a CH4O* intermediate before complete energy randomization was identified as producing OH at the intermediate rate and was associated with a population distribution with more rovibrational energy than the slow mechanism. The third mechanism produces OH promptly with a cold rovibrational distribution, indicative of a collinear abstraction mechanism. After these identifications were made, it was possible to predict the fraction of signal associated with each mechanism at different probe wavelengths in the ultrafast experiment, and the predictions proved consistent with measured appearance signals. This model also reconciles data from a variety of previous experiments. While this model is the simplest that is consistent with the data, it is not definitive for several reasons. First, the appearance signals measured in these experiments probe simultaneously many OH(v,J,Ω,Λ) states, which would tend to obfuscate differences in the appearance rate of specific rovibrational states. Second, only about half of the OH(v,J,Ω,Λ) states populated by this reaction could be probed by laser-induced fluorescence through the OH A←X band with our apparatus. Third, the cluster environment might influence the dynamics compared to the free bimolecular reaction.

Notes: Quantum mechanical calculations on the vibrational predissociation dynamics of NeBr2 in the B electronic state have been performed and the results compared with both experimental data and other computational studies. For vibrational levels with v≤20 we find that the vibrational state dependence of the predissociation lifetimes is in qualitative agreement with experimental measurements, as are the calculated Br2 fragment rotational distributions. For higher vibrational levels, the B←X excitation profiles are well represented by a sum of two Lorentzian line shapes. We attribute this result to the presence of long-lived resonances in the dissociative continuum that are reminiscent of long-lived dissociative trajectories in previous classical studies of NeBr2. © 2000 American Institute of Physics.

Notes: The rotational level distribution of the NO fragments formed as a result of the predissociation of the vibrationally excited NO–C2H4 (ν7) van der Waals molecule was measured by laser excited fluorescence techniques. The distribution was found to be Boltzmann in character, described by the rotational temperature 75±15 K. An average kinetic energy release of ≈105 cm−1 per fragment, in an isotropic flux distribution, was determined from Doppler profiles of the NO fragments in selected rotational levels.