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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5538-5540 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report the first spectroscopic characterization of any triplet Rydberg state of the imidogen radical. The B 3Π state of NH and ND is identified via the two photon resonance enhancement it provides in the MPI spectrum of ground (X 3Σ−) state NH(ND) radicals, and shown to be well described (at least near its equilibrium geometry) as a 3p Rydberg state built on the ground (X 2Π) state ion core. We consider also the origin of an overlapping 3Σ−X 3Σ− two photon resonance apparent only in the spectrum of the ND radical.
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 3157-3165 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The technique of H(D) atom photofragment translational spectroscopy has been applied to the photodissociation of HCN(DCN) at 121.6 nm. Analyses of the H(D) atom time-of-flight spectra reveal the partner CN fragment to be formed predominantly in its A 2Π excited electronic state. Branching into the H/D+CN(B 2∑+) product channel accounts for a few percent of the total fragment yield, but we discern no evidence for any contribution from the product channel yielding H/D atoms in conjunction with ground state CN(X 2∑+) fragments. The majority of the CN (A) fragments are formed in their v'=0 level but with a markedly bimodal rotational state population distribution. This bimodality has been rationalized in the light of the available information regarding the form of the potential energy surface of the excited 1Π state of HCN(DCN) populated following photoexcitation at 121.6 nm.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 7064-7072 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Five new triplet excited states of the ND radical (three in the case of NH) in the wave-number range 85 000–91 000 cm−1 have been identified through analysis of the two-photon resonance enhancements they provide to the wavelength-resolved multiphoton ionization spectrum of X 3Σ− state NH(ND) radicals. The lowest energy of these, the B 3Π state, is found to be a "regular'' Rydberg state which, on the basis of its observed quantum defect and its deduced rotational and spin–orbit coupling constant, is surmised to be the 3Π state derived from a 3pσ electron built on the 2Π ground-state ion core. Perturbations are evident in the B 3Π–X 3Σ− origin bands of both NH and ND. In the case of ND the perturbing state provides its own resonance enhancements, the analysis of which enables its definitive identification as the C 3Σ− state. The very small spin–orbit splitting found for the D 3Π state is taken to indicate that (at least in the Franck–Condon region) its wave function is dominated by the configuration involving one 3pπ Rydberg electron and a 4Σ− ion core. To still higher wave number we identify two more 3Σ− excited states, the upper of which (the F 3Σ− state) has a very small rotational constant which we take to imply that it has substantial valence character. Further indications that the F 3Σ− (and C 3Σ−) states possess significant valence character is provided by the observation that both parent and daughter (N+) ions contribute to the overall ion yield when the multiphoton ionization proceeds via these two states. Daughter-ion formation is considered to occur via an overall four-photon excitation process in which the coherent two-photon excitation to the 3Σ− state of interest is followed by a one-photon excitation to a "superexcited'' state of the neutral. This is then presumed to absorb a further photon to yield the observed N+ ions and/or to predissociate, yielding highly excited N* atoms which then undergo a direct one-photon ionization.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 4195-4204 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rovibrational state distribution of the nascent NH2(A˜ 2A1) fragments generated by 193.3 nm photodissociation of a room temperature sample of NH3 is determined through an analysis of a major portion (6000–13 000 cm−1) of the NH2(A˜ 2A1→X˜ 2B1) near infrared emission spectrum obtained by time-resolved Fourier transform infrared emission spectroscopy. The NH2(A˜) fragments are observed to be formed predominantly in their zero-point vibrational level, with substantial rotational excitation about their a-inertial axis up to the limit of the available energy, ∼3150 cm−1, but with little excitation about the other axes. The pattern of this energy disposal is discussed within the framework of existing knowledge regarding the form of the NH3 A˜ state potential energy surface on which the dissociation occurs. The essential features are entirely consistent with a direct carry over, into the fragment, of the out-of-plane bending vibrational motion introduced in the parent molecule by the photoexcitation process.
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  • 5
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 92 (2002), S. 672-681 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Resonance enhanced multiphoton ionization and cavity ring down spectroscopies have been used to provide spatially resolved measurements of relative H atom and CH3 radical number densities, and NH column densities, in a hot filament (HF) reactor designed for diamond chemical vapor deposition and here operating with a 1% CH4/n/H2 gas mixture—where n represents defined additions of N2 or NH3. Three-dimensional modeling of the H/C/N chemistry prevailing in such HF activated gas mixtures allows the relative number density measurements to be placed on an absolute scale. Experiment and theory both indicate that N2 is largely unreactive under the prevailing experimental conditions, but NH3 additions are shown to have a major effect on the gas phase chemistry and composition. Specifically, NH3 additions introduce an additional series of "H-shift" reactions of the form NHx+H(r harp over l)NHx−1+H2 which result in the formation of N atoms with calculated steady state number densities 〉1013 cm−3 in the case of 1% NH3 additions in the hotter regions of the reactor. These react, irreversibly, with C1 hydrocarbon species forming HCN products, thereby reducing the concentration of free hydrocarbon species (notably CH3) available to participate in diamond growth. The deduced reduction in CH3 number density due to competing gas phase chemistry is shown to be compounded by NH3 induced modifications to the hot filament surface, which reduce its efficiency as a catalyst for H2 dissociation, thus lowering the steady state gas phase H atom concentrations and the extent and efficiency of all subsequent gas phase transformations. © 2002 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 91 (2002), S. 3605-3613 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Chemical vapor deposition (CVD) has been used to grow sulfur doped diamond films on undoped Si and single crystal HPHT diamond as substrates, using a 1% CH4/H2 gas mixture with various levels of H2S addition (100–5000 ppm), using both microwave (MW) plasma enhanced CVD and hot filament (HF) CVD. The two deposition techniques yield very different results. HFCVD produces diamond films containing only trace amounts of S (as analyzed by x-ray photoelectron spectroscopy), the film crystallinity is virtually unaffected by gas phase H2S concentration, and the films remain highly resistive. In contrast, MWCVD produces diamond films with S incorporated at levels of up to 0.2%, and the amount of S incorporation is directly proportional to the H2S concentration in the gas phase. Secondary electron microscopy observations show that the crystal quality of these films reduces with increasing S incorporation. Four point probe measurements gave the room temperature resistivities of these S-doped and MW grown films as ∼200 Ω cm, which makes them ∼3 times more conductive than undoped diamond grown under similar conditions. Molecular beam mass spectrometry has been used to measure simultaneously the concentrations of the dominant gas phase species present during growth, for H2S doping levels (1000–10 000 ppm in the gas phase) in 1% CH4/H2 mixtures, and for 1% CS2/H2 gas mixtures, for both MW and HF activation. CS2 and CS have both been detected in significant concentrations in all of the MW plasmas that yield S-doped diamond films, whereas CS was not detected in the gas phase during HF growth. This suggests that CS may be an important intermediary facilitating S incorporation into diamond. Furthermore, deposition of yellow S was observed on the cold chamber walls when using H2S concentrations 〉5000 ppm in the MW system, but very little S deposition was observed for the HF system under similar conditions. All of these results are rationalized by a model of the important gas phase chemical reactions, which recognizes the very different gas temperature profiles within the two different types of deposition reactor.© 2002 American Institute of Physics.
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  • 7
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 89 (2001), S. 697-709 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The plume accompanying 193 nm pulsed laser ablation of graphite in vacuum has been studied using wavelength, time and spatially resolved optical emission spectroscopy and by complementary Faraday cup measurements of the positively charged ions. The temporal and spatial extent of the optical emissions are taken as evidence that the emitting species result from electron–ion recombination processes, and subsequent radiative cascade from the high n,l Rydberg states that result. The distribution of C neutral emission is symmetric about the surface normal, while the observed C+ emission appears localized in the solid angle between the laser propagation axis and the surface normal. However, Faraday cup measurements of the ion yield and velocity distributions, taken as a function of scattering angle and incident pulse energy, indicate that the total ion flux distribution is peaked along the surface normal. The derived ion velocity distributions are used as input for a two-dimensional model which explains the observed anisotropy of the C+ emission in terms of preferential multiphoton excitation and ionization of C species in the leading part of the expanding plasma ball that are exposed to the greatest incident 193 nm photon flux, prior to electron–ion recombination and subsequent radiative decay. © 2001 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 84 (1998), S. 1618-1625 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Field emission properties of undoped chemical vapor deposited diamond and diamond-like carbon films have been measured for a variety of different deposition conditions. The nature and appearance of the damage site after testing has been investigated with scanning electron microscopy and laser Raman mapping. These observations, together with the mathematical form of the observed current–voltage relations, are correlated with the conductivity of the film. The results are consistent with a model for the overall emission current that combines conduction mechanisms through the bulk of the film with Fowler–Nordheim tunneling. © 1998 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 89 (2001), S. 5219-5223 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The boundaries of the diamond deposition region in the C–H–O (Bachmann) atomic phase composition diagram have been reproduced successfully for 38 different C, H, and O containing gas mixtures using the CHEMKIN computer package, together with just two criteria—a minimum mole fraction of methyl radicals [CH3] and a limiting value of the [H]/[C2H2] ratio. The diamond growth/no-growth boundary coincides with the line along which the input mole fractions of C and O are equal. For every gas mixture studied, no-growth regions are found to coincide with a negligible (〈10−10) mole fraction of CH3 radicals, while for gas mixtures lying within the diamond growth region the CH3 mole fraction is ∼10−7. Each no-growth→diamond growth boundary is seen to be accompanied by a 2–3 order of magnitude step in CH3 mole fraction. The boundary between diamond and nondiamond growth is less clearly defined, but can be reproduced by assuming a critical, temperature dependent [H]/[C2H2] ratio (0.2, in the case that Tgas=2000 K) that reflects the crucial role of H atoms in the etching of nondiamond phases. The analysis allows prediction of the composition process window for good quality diamond growth for all stable input gas mixtures considered in this study. © 2001 American Institute of Physics.
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  • 10
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Microwave plasma enhanced chemical vapor deposition has been used to grow diamond films at substrate temperatures down to 435 °C using CO2/CH4 gas mixtures. An Arrhenius plot of growth rate as a function of substrate temperature yields a value for the activation energy for the growth step of 28 kJ mol−1. This is lower than that measured previously for CH4/H2 systems and hints at a different gas-surface chemistry when using CH4/CO2 plasmas. Molecular beam mass spectrometry has been used to measure simultaneously the concentrations of the dominant gas phase species present during growth, for a wide range of plasma gas mixtures (0%–80% CH4, balance CO2). The CHEMKIN computer package has also been used to simulate the experimental results in order to gain insight into the major reactions occurring within the microwave plasma. The calculated trends for all species agree well with the experimental observations. Using these data, the model for the gas phase chemistry can be reduced to only four overall reactions. Our findings suggest that CH3 radicals are likely to be the key growth species when using CO2/CH4 plasmas and provide a qualitative explanation for the narrow concentration window for diamond growth. © 2001 American Institute of Physics.
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