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  • 1
    Electronic Resource
    Electronic Resource
    Matrix isolation study of the interaction of excited neon atoms with CCl4: Infrared spectra of the ion products and of Cl2CCl⋅⋅Cl (1998)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 7147-7156 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: When a Ne:CCl4 sample is codeposited at approximately 5 K with a beam of neon atoms that have been excited in a microwave discharge, the infrared spectrum of the resulting deposit includes prominent absorptions not only of CCl3 but also of several other neutral and ionic species. The absorptions assigned to CCl3+, CCl2+, and CCl+ are consistent with previous spectroscopic identifications of these species. As at lower energies, the Cl2CCl⋅⋅Cl isomer of CCl4 contributes to the product spectrum. Higher level ab initio calculations of the fundamental vibrations of this isomer and of its carbon-13 substituted counterpart give improved agreement with the experimentally observed infrared spectrum and, together with the results of a supplementary experiment, provide further support for the assignment of a structured absorption near 500 cm−1 to this species, rather than to Cl3+. Uncharged Cl2CCl⋅⋅Cl is readily destroyed by visible radiation, with concomitant growth in the absorptions of CCl4. Photodestruction of ionic species occurs in the ultraviolet spectral region. Evidence is presented for the stabilization of Cl2CCl⋅⋅Cl− and of Cl3CCl− in these experiments. The latter species undergoes photodestruction in the near infrared spectral region. Two absorptions are tentatively assigned to the ClCCl⋅⋅Cl− fragment ion.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.477397
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  • 2
    Electronic Resource
    Electronic Resource
    Vibrational spectra of molecular ions isolated in solid neon. XV. Infrared spectroscopic evidence for NeHF+ and HFFH+ (1999)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 5037-5046 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: When a Ne:HF mixture is subjected to Penning ionization and/or photoionization by neon atoms in their first excited states, between 16.6 and 16.85 eV, and the products are rapidly frozen at approximately 5 K, the infrared spectrum of the resulting deposit includes absorptions assigned to NeHF+ and HFFH+. Evidence is presented suggesting that neon-matrix shifts may be anomalously large for protonated molecules which are derived from species with proton affinities near or below 550 kJ/mol. The results of earlier ab initio studies, as well as those of the present experimental and ab initio studies, indicate that the NeHF+ complex is quite strongly bound. The ν3 absorptions of NeHF+ and NeDF+ and the ν1+ν3 absorption of NeHF+ are tentatively identified. An absorption at 3064.7 cm−1 has isotopic substitution behavior appropriate for its assignment to HFFH+. Density functional calculations were performed in order to estimate the positions of the harmonic vibrational fundamentals of HFFH+-dn, and a more elaborate two-dimensional calculation on the HF-stretching potential surface was conducted in an attempt to take into account the large anharmonic contribution. Processes which occur on ultraviolet irradiation of the deposit are considered. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.478402
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  • 3
    Electronic Resource
    Electronic Resource
    Spectroscopy of the fluoromethylene radicals HCF and DCF by 2+1 resonance enhanced multiphoton ionization spectroscopy and by ab initio calculation (1995)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 1303-1308 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Spectra of fluoromethylene radicals, HCF and DCF, have been observed between 304 and 325 nm using mass-resolved, resonance enhanced multiphoton ionization (REMPI). Singlet HCF is generated by sequential reactions of atomic fluorine in either methane or methyl fluoride. The spectra arise from two-photon resonances between the ground state X˜ 1A′ and the previously unobserved E˜ 1A′ (3p) Rydberg state. The band origins lie at T0=62154±2 cm−1 (321.69±0.01 nm) and T0=62175±2 cm−1 (321.58±0.01 nm) (2σ) above the ground states for HCF and DCF, respectively. Vibrational resolution and partial rotational resolution are obtained, with ν2′=1128±4 cm−1 and ν3′=1614±4 cm−1 for HCF and ν1′=2095±5 cm−1, ν2′=872±3 cm−1, and ν3′=1582±4 cm−1 for DCF (2σ). Under typical experimental conditions, the strongest peak for HCF is due to the 210310 resonance at 308.23±0.04 nm and the strongest peak for DCF is due to the 220 resonance at 312.85±0.01 nm. The results of vibrational and rotational analyses are consistent with predictions from ab initio calculations, which also yield the adiabatic ionization potential IPa=10.06±0.05 eV (2σ).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.469807
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  • 4
    Electronic Resource
    Electronic Resource
    Detection and characterization of gas-phase InCl using resonance enhanced multiphoton ionization (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 3422-3428 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report resonance enhanced multiphoton ionization (REMPI) spectra of gas-phase indium monochloride (InCl) between 330 and 490 nm. The spectra originate from one-, two-, and three-photon resonances with electronic states that reside between 27 000 and 75 000 cm−1. We assign 12 new Rydberg states. From these Rydberg origins we can extrapolate the adiabatic ionization potential IPa=77 460±600 cm−1 (9.60±0.08 eV). The Rydberg states exhibit vibrational frequencies ranging between 307 and 355 cm−1.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.467246
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  • 5
    Electronic Resource
    Electronic Resource
    Two photon resonance enhanced multiphoton ionization spectroscopy of gas phase O2 a 1Δg between 305–350 nm (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 1977-1981 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The resonance enhanced multiphoton ionization (REMPI) spectrum of O2 a 1Δg between 305 and 350 nm is reported. The spectrum is compared to the REMPI spectrum of ground state molecular oxygen in the same electronic energy region, and a number of differences in the respective spectra are observed. Detection limits for O2 a 1Δg by REMPI is calculated to be 5×109 molecule cm−3 in the ion source of the mass spectrometer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.453170
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  • 6
    Electronic Resource
    Electronic Resource
    Infrared photodissociation of benzene dimers in the 1000 cm−1 frequency region (1986)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 2624-2629 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The infrared photodissociation of benzene dimers has been investigated in the frequency region of the CO2 laser. A single absorption peak is observed with a maximum at 1038 cm−1, and a full width at half-maximum of about 2 cm−1. The laser fluence dependence of the dissociation yield and two-laser hole burning experiments both indicate that the linewidth is mostly homogeneous. The benzene monomer fragments from the photodissociation emerge with an isotropic angle distribution. A relatively large fraction of the available energy goes into product translation, and the remainder into rotation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.450333
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  • 7
    Electronic Resource
    Electronic Resource
    Aluminum monochloride excited states observed by resonance-enhanced multiphoton ionization spectroscopy (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 7521-7528 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: AlCl was detected and characterized with 1+2, 2+1, 2+2, 3+1, and 3+2 resonance-enhanced multiphoton ionization spectroscopy using laser light between 332 and 570 nm. AlCl was generated in the gas phase with high temperature reaction of Al with InCl3, or by the reaction of Al with AgCl. New states residing between 52 000 and 66 000 cm−1 were identified. Vibrational intervals of the new Rydberg states are about 20% greater than those of AlCl (X 1Σ+), with most lying between 565–595 cm−1.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465682
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  • 8
    Electronic Resource
    Electronic Resource
    Electronic spectra of the heteroisotopic CH2D and CHD2 radicals by resonance enhanced multiphoton ionization (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 3732-3736 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The 3p 2B1←←X˜ 2B1 bands of CH2D and CHD2 radicals were observed between 305 and 335 nm by mass resolved, 2+1 resonance enhanced multiphoton ionization spectroscopy. Spectroscopic constants were found for the 3p 2B1 Rydberg state of the CH2D radical (ν00=59 940 cm−1, ν1a1 CH2 stretch=2995 cm−1, ν2a1 CD stretch=2220 cm−1, ν4b1 out-of-plane large amplitude (OPLA)=1260 cm−1, ν5b2 CH2 asymmetric stretch=3055 cm−1, ν6b2 CD bend=1115 cm−1) and of the CHD2 radical (ν00=59 920 cm−1, ν1a1 CH stretch=3040 cm−1, ν2a1 CD2 stretch=2150 cm−1, ν4b1 OPLA=1165 cm−1, ν6b2 CH bend=1210 cm−1). Vibrational frequencies calculated by ab initio theory agree well with the experimental data.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.464051
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  • 9
    Electronic Resource
    Electronic Resource
    New electronic spectra of the CHFCl radical observed with resonance enhanced multiphoton ionization (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 1925-1932 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The structures and optical spectroscopy of the CHFCl radical and cation were studied by ab initio molecular orbital calculations and by experiment. Ab initio calculations at the MP2/ 6–311++G** theory level found that the optimum structure of the CHFCl+ (X˜ 1A') cation is planar with r(C–H)=1.092 A(ring), r(C–F)=1.254 A(ring), r(C–Cl)=1.599 A(ring), (angle)H–C–F=116.85°, and (angle)H–C–Cl=122.14°. CHFCl (X˜ 2A') radical is nonplanar with r(C–H)=1.083 A(ring), r(C–F)=1.335 A(ring), r(C–Cl)=1.705 A(ring), (angle)H–C–F=113.49°, (angle)H–C–Cl=116.68°, and (angle)F–C–Cl=114.44°. The ab initio angle between the F–C–Cl plane and the C–H bond is Φe=38° and the inversion barrier is Binv=1190 cm−1. Using isogyric reactions to obtain empirical corrections, we calculate IPa(CHFCl)=8.37±0.05 eV. Ab initio vibrational frequencies are reported. The electronic spectrum of the CHFCl radicals was observed between 340–420 nm using one color, mass resolved, 2+1 resonance enhanced multiphoton ionization (REMPI) spectroscopy. The spectrum arises from two-photon resonances with the planar F˜(3p) [λlaser=406.7 nm, ν00=49 160(20) cm−1] and J(3d) [λlaser=361.9 nm, ν00=55 250(20) cm−1] Rydberg states. A third laser photon ionized the radicals. Both states produced the same vibrational constants: ν2 (C–H deformation)=1280(30) cm−1, ν4 (C–Cl stretch)=910(30) cm−1, ν5 (CFCl scissors)=440(30) cm−1, ν6 (OPLA)=980(30) cm−1. The REMPI spectrum exhibited v‘6 = 1–6 hot bands of the CHFCl (X˜ 2A) radical. Modeling of these hot bands with a double-well potential gives the inversion barrier, Binv=1180 cm−1, and Φe=42°.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.464226
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  • 10
    Electronic Resource
    Electronic Resource
    Triplet Rydberg states of the imidogen radical characterized via two-photon resonance-enhanced multiphoton ionization spectroscopy (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 7064-7072 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.463532
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