Infrared fluorescence from PAHs in the laboratory

Several celestial objects, including UV rich regions of planetary and reflection nebulae, stars, H II regions, and extragalactic sources, are characterized by the unidentified infrared emission bands (UIR bands). A few years ago, it was proposed that polycyclic aromatic hydrocarbon species (PAHs) are responsible for most of the UIR bands. This hypothesis is based on a spectrum analysis of the observed features. Comparisons of observed IR spectra with lab absorption spectra of PAHs support the PAH hypothesis. An example spectrum is represented, where the Orion Bar 3.3 micron spectrum is compared with the absorption frequencies of the PAHs Chrysene, Pyrene, and Coronene. The laser excited 3.3 micron emission spectrum is presented from a gas phase PAH (azulen). The infrared fluorescence theory (IRF) is briefly explained, followed by a description of the experimental apparatus, a report of the results, and discussion

Plant species first recognised as naturalised for New South Wales in 2002 and 2003, with additional comments on species recognised as naturalised in 2000–2001

Information is provided on the taxonomy and distribution of 71 taxa of naturalised or naturalising plants newly recorded for the state of New South Wales during the period 1 January 2002 to 31 December 2003. Of these taxa, 32 are new records for Australia (prefaced with a †). These species are: Abutilon pictum, Acanthus mollis, †Aesculus indica (naturalising), Agapanthus praecox subsp. orientalis, Ajuga reptans, †Anigozanthos flavidus, Aquilegia vulgaris, Arbutus unedo, †Athertonia diversifolia (naturalising), †Bergenia x schmidtii (naturalising), Bromus catharticus subsp. stamineus, Bryophyllum daigremontianum, Bryophyllum fedtschenkoi, Calyptocarpus vialis, †Ceiba speciosa (naturalising), Cereus uruguayanus, †Cestrum x cultum, †Chamaecyparis lawsoniana, Cistus salviifolius, †Clematis montana, †Coprosma x cunninghamii, Coprosma robusta, Cornus capitata, Cotoneaster simonsii, Cotoneaster x watereri group, Crinum moorei, Cupressus lusitanica, †Cylindropuntia fulgida var. mamillata forma monstrosa, †Cylindropuntia prolifera, Cylindropuntia tunicata, Desmanthus virgatus, Drosanthemum candens, †Elaeagnus umbellata (naturalising), †Eragrostis trichophora, †Eupatorium lindleyanum, †Gibasis pellucida, Glechoma hederacea, †Hesperis matronalis, Hieracium aurantiacum subsp. carpathicola, †Inga edulis (naturalising), †Juniperus conferta (naturalising), †Justicia caudata, Lamium galeobdolon, Lathyrus tingitanus, †Lysimachia fortunei, †Maackia amurensis, †Monstera deliciosa, †Murdannia keisak, Odontonema tubaeforme, Oxalis vallicola, Phoenix canariensis, †Physostegia virginiana, Pinus patula, Pittosporum eugenioides, †Pittosporum ralphii, Pittosporum tenuifolium, Plectranthus ecklonii, †Potentilla vesca, †Prunus campanulata, †Rhododendron ponticum, Rosa luciae, Rubus rugosus, Ruellia squarrosa, †Senna multijuga, Stapelia gigantea, Stephanophysum longifolium, Strobilanthes anisophylla, †Tabebuia chrysotricha, †Tabebuia impetiginosa, †Tradescantia pallida and Ulmus x hollandica. Additional notes and name changes are recorded for plants first recognised as naturalised for New South Wales over the period 2000–2001. The identification of several naturalised taxa occurring in New South Wales has been corrected. Plants formerly identified as Pinus nigra var. corsicana are now considered to be Pinus halepensis; Cylindropuntia arbuscula is Cylindropuntia kleiniae, Cylindropuntia tunicata is Cylindropuntia rosea, Abrus precatorius subp. precatorius is now Abrus precatorius subsp. africanus and Cotoneaster ?horizontalis is Cotoneaster microphyllus. Further field studies have revealed that Cylindropuntia leptocaulis, Cylindropuntia spinosior, Hypericum kouytchense and Chamaesyce ophthalmica are more widespread than previously thought

Energy‐dependent collisional deactivation of vibrationally excited azulene

Collisional energy transfer parameters for highly vibrationally excited azulene have been deduced from new infrared fluorescence (IRF) emission lifetime data with an improved calibration relating IRF intensity to vibrational energy [J. Shi, D. Bernfeld, and J. R. Barker, J. Chem. Phys. 88, 6211 (1988), preceding paper]. In addition, data from previous experiments [M. J. Rossi, J. R. Pladziewicz, and J. R. Barker, J. Chem. Phys. 78, 6695 (1983)] have been reanalyzed based on the improved calibration. Inversion of the IRF decay curves produced plots of energy decay, which were analyzed to determine 〈ΔE〉, the average energy transferred per collision. Master equation simulations reproduced both the original IRF decays and the deduced energy decays. A third (simple) method of 〈ΔE〉 determination agrees well with the other two. The results show 〈ΔE〉 to be nearly directly proportional to the vibrational energy of the excited azulene from ∼8000 to 33 000 cm−1. At high energies, there are indications that the 〈ΔE〉 energy dependence may be slightly reduced.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/69999/2/JCPSA6-88-10-6219-1.pd

Collisional deactivation of highly vibrationally excited pyrazine

The collisional deactivation of vibrationally excited pyrazine (C4N2H4) in the electronic ground state by 19 collider gases was studied using the time‐resolved infrared fluorescence (IRF) technique. The pyrazine was photoexcited with a 308 nm laser and its vibrational deactivation was monitored following rapid radiationless transitions to produce vibrationally excited molecules in the electronic ground state. The IRF data were analyzed by a simple approximate inversion method, as well as with full collisional master equation simulations. The average energies transferred in deactivating collisions (〈ΔE〉d) exhibit a near‐linear dependence on vibrational energy at lower energies and less dependence at higher energies. The deactivation of ground state pyrazine was found to be similar to that of ground state benzene [J. R. Barker and B. M. Toselli, Int. Rev. Phys. Chem. 12, 305 (1990)], but it is strikingly different from the deactivation of triplet state pyrazine [T. J. Bevilacqua and R. B. Weisman, J. Chem. Phys. 98, 6316 (1993)]. © 1996 American Institute of Physics.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/70797/2/JCPSA6-105-4-1383-1.pd

Reactant states model: Predicted k(E,J) for NO2(2A1)→O(3P)+NO(2Π), based on spectroscopic data

High‐order spectroscopic data for the reactant are used exclusively to determine both the sum of open reactive channels and the density of states, which are used in a statistical theory to predict dissociation rate constants. Practical methods are introduced for calculating sums of reactive channels and densities of states, when couplings among all degrees of freedom are included. An empirical method is described for reconciling spectroscopic parameters with known dissociation energies (also determined spectroscopically). The predicted k(E,J)’s and thermal k∞(T) for NO2 dissociation are in good agreement with experimental data, especially when the effects of electronically excited states are included. The predicted low pressure thermal rate constants are generally in fair agreement with experiment, although a slightly different temperature dependence is calculated; this discrepancy is probably due to the absence of unknown higher order spectroscopic terms and to the crude corrections made for excited electronic states. When high order spectroscopic (or theoretical) data are available and when the effects due to excited electronic states are considered, this theory is useful for predicting, fitting, and interpreting unimolecular rate data.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/70846/2/JCPSA6-91-4-2239-1.pd

Excitation of CO2 by energy transfer from highly vibrationally excited benzene derivatives

The time‐resolved infrared fluorescence technique has been used to study V–V and V–T/R energy transfer to carbon dioxide from highly excited benzene, benzene‐d6, toluene, and toluene‐d8. The highly vibrationally excited aromatics in the electronic ground state are obtained by radiationless transitions after pumping with a KrF laser at 248 nm to the S1 excited electronic level. The V–V energy transfer from the excited parent to the asymmetric stretch mode of CO2 was measured by observing the characteristic emission of CO@B|2 near 4.3 μm. From these measurements, the probability per collision of formation of CO∗2 was determined as a function of the internal energy in the excited aromatic. In all cases investigated, this probability is ≤0.1% at the initial excitation energy of 40 000 cm−1 and it is approximately directly proportional to the vibrational energy of the excited aromatic. The total concentration of CO@B|2 produced as a result of the many collisions needed to totally deactivate the excited aromatic amounted to >5% of the initial concentration of the excited aromatic and the quantitative values obtained are in excellent agreement with other work.A simple dipole–dipole interaction model is shown to explain the observed magnitude of V–V energy transfer and it is used to predict the amount of energy transferred to the bending mode of CO2. A key feature of this model is that the states of the highly vibrationally excited polyatomic are assumed to be broadened by rapid intramolecular vibrational redistribution of energy. In addition to the V–V energy‐transfer measurements, the average energy lost per collision by the excited aromatic was determined as a function of the vibrational energy of the aromatic, and the rate constants were determined for CO∗2 deactivation by the nondeuterated species. For the deuterated species, the results implicated a contribution from resonant V–V transfer between the C–D stretch modes and the asymmetric stretch mode of CO2. The overall results for the CO2 collider gas indicate that V–V energy transfer contributes a relatively small portion of the total energy transfer, and that portion can be described with the dipole–dipole interactions model.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/71252/2/JCPSA6-95-11-8108-1.pd

Energy dependence of infrared emission from azulene C–H stretching vibrations

New data are described on the energy dependence of infrared fluorescence (IRF) from the C–H stretch modes (∼3050 cm−1) of vibrationally excited azulene (C10H8). An optoacoustic method was used to measure the absorbed laser energy and determine the number of excited molecules, while time‐resolved infrared emission was recorded. The experimental uncertainties of ∼5% are much smaller than in previous work and the agreement between the experiments and the theory for the IRF intensity is excellent for total vibrational energies from 14 000 to 33 000 cm−1.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/70442/2/JCPSA6-88-10-6211-1.pd

Study of Local Power Dissipation in Ultrascaled Silicon Nanowire FETs

The local electron power dissipation has been calculated in a field-effect nanowire transistor using a quantum transport formalism. Two different channel cross sections and optical and acoustic phonon mechanisms were considered. The phonon models used reproduce the phonon limited mobility in the cross sections studied. The power dissipation for different combinations of source, channel, and drain dimensions have been calculated. Due to the lack of complete electron energy relaxation inside the device, the Joule heat dissipation over-estimates the power dissipated in small nanotransistors. This over-estimation is larger for large cross sections due to the weaker phonon scattering. On the other hand, in narrow wires, the power dissipation inside the device can be large, therefore, mitigating against fabrication of very narrow nanowire transistors. We have also investigated the cooling of the device source region due to the mismatch of the Peltier coefficients between the source and the channel

Temperature effects in the collisional deactivation of highly vibrationally excited pyrazine by unexcited pyrazine

Time‐dependent infrared fluorescence (IRF) from the C–H fundamental and overtone bands was used to monitor the vibrational deactivation (by unexcited pyrazine) of pyrazine excited at 308 nm with a pulsed laser. The 1‐color and 2‐color IRF results were modeled with collisional master equation calculations in order to determine the temperature dependence of the energy transfer parameters. The experimental data cannot be modeled without invoking a biexponential collision step size distribution, which implies that ‘‘super collisions’’ are significant. The results show that the energy transfer parameters are essentially constant at temperatures greater than the Lennard–Jones well depth, but at lower temperatures, energy transfer is enhanced. It is likely that vibration–vibration energy transfer dominates in this system. © 1996 American Institute of Physics.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/70488/2/JCPSA6-105-8-3012-1.pd