Hiroyuki Ozeki

Vibronic coupling in the ground cationic state of naphthalene: A laser threshold photoelectron [zero kinetic energy (ZEKE)‐photoelectron] spectroscopic study

The two‐color (1+1’) threshold photoelectron spectra of naphthalene in a supersonic free jet have been recorded via nine vibronic levels of the S1 electronic state up to about 1420 cm−1 above the S1 band origin. The threshold photoelectron spectra recorded via the S1 band origin and via totally symmetric ag vibronic levels show significant intensity in Δν=+1 transitions in nontotally symmetric vibrations having b1g symmetry indicating that the ionization transition gains significant intensity through a vibronic coupling mechanism between the two lowest doublet cationic states. The strongest departure from the expected Δν=0 propensity in the threshold photoelectron spectra occurs through excitation of the totally symmetric 8 mode having ag symmetry indicating that a considerable displacement occurs along the normal coordinate of this 8 mode upon ionization from the S1 state. The superior resolution of the threshold photoelectron technique over conventional photoelectron methods has allowed accurate values for the fundamental vibrational frequencies of naphthalene in its ground cationic state to be determined and it has also allowed a more rigorous investigation of the vibronic coupling mechanism that occurs between the two lowest doublet cationic states. Moreover, an improved value for the adiabatic ionization energy of naphthalene of 65 687±7 cm−1 (8.1442±0.0009 eV) has been determined.The two‐color (1+1’) threshold photoelectron spectra of naphthalene in a supersonic free jet have been recorded via nine vibronic levels of the S1 electronic state up to about 1420 cm−1 above the S1 band origin. The threshold photoelectron spectra recorded via the S1 band origin and via totally symmetric ag vibronic levels show significant intensity in Δν=+1 transitions in nontotally symmetric vibrations having b1g symmetry indicating that the ionization transition gains significant intensity through a vibronic coupling mechanism between the two lowest doublet cationic states. The strongest departure from the expected Δν=0 propensity in the threshold photoelectron spectra occurs through excitation of the totally symmetric 8 mode having ag symmetry indicating that a considerable displacement occurs along the normal coordinate of this 8 mode upon ionization from the S1 state. The superior resolution of the threshold photoelectron technique over conventional photoelectron methods has allowed accurate values ...

A new high-resolution threshold photoelectron analyzer : observation of rotational structure of NO+ cation

Abstract A new compact analyzer has been designed and constructed for the purpose of detecting threshold photoelectrons through a capillary plate. Two-color (1 + 1′) REMPI experiments have been carried out on jet-cooled NO via the A 2 Σ + state ( v ′ = 0, N ′ = 7). The resulting threshold photoelectron spectrum was obtained with a resolution of 4 cm −1 , showing seven “rotational peaks“ due to the v + = 0, N + = 4–10 levels of NO + ( 1 Σ + ) produced by ionization transitions of δ N = 0, ±1, ±2 and ±3.

Observations of NH2D toward Dark Molecular Clouds

The 1-1 transition of NH2D at 110.1536 GHz was surveyed toward 16 cores of high ammonia abundance in 14 cold dark clouds and was detected toward eight cloud cores, L1448, B1, L1489N, L1551N, L1641N, L134N(S), ρ Oph E, and L63, where L134N and L63 are not associated with infrared sources. The column densities of NH2D were compared with those of the main species NH3, previously determined for the corresponding sources, and the relative abundance, [NH2D]/[NH3], was found to be large, 0.025-0.18, which is among the highest deuterium fractionation so far observed. The relative abundance is remarkably larger than a predicted value by the latest gas-phase chemical model for dark clouds by Howe & Millar. The spectral line of NH2D was not detected in other dark cloud cores. These results suggest that a part of NH3 in dark clouds could originate from dust related reactions associated with energetic events.

Atomic carbon and CO isotope emission in the vicinity of DR 15

We present observations of the P-3(1)-P-3(o) fine-structure transition of atomic carbon [C I], the J = 3-2 transition of CO, and the J = 1-0 transitions of (CO)-C-13 and (CO)-O-18 toward DR 15, an H II region associated with two mid-infrared dark clouds (IRDCs). The (CO)-C-13 and (CO)-O-18 J = 1-0 emissions closely follow the dark patches seen in optical wavelength, showing two self-gravitating molecular cores with masses of 2000 and 900 M-circle dot, respectively, at the positions of the cataloged IRDCs. Our data show a rough spatial correlation between [C I] and (CO)-C-13 J = 1-0. Bright [C I] emission occurs in the relatively cold gas behind the molecular cores but does not occur in either highly excited gas traced by CO J = 3-2 emission or in the H II region/molecular cloud interface. These results are inconsistent with those predicted by standard photodissociation region models, suggesting an origin for interstellar atomic carbon unrelated to photodissociation processes.

Microwave spectroscopic detection of transition metal hydroxides: CuOH and AgOH

Pure rotational spectra of transition metal hydroxides have been reported. Millimeter wave spectra of CuOH and AgOH were recorded in a direct current discharge absorption cell in the range of 200–390 GHz. The spectra of both molecules correspond to that of a near prolate asymmetric top and only a-type R branch transitions were observed. The rotational and centrifugal distortion constants of CuOH and AgOH were precisely determined. Centrifugal distortion terms up to N2Nz10 were required to fit the observed line frequencies of 63CuOH. A preliminary analysis showed that AgOH is also strongly bent like CuOH with a bond angle smaller by about 2°.

Microwave spectra of CuOD and AgOD: Molecular structure and harmonic force field of CuOH and AgOH

Pure rotational spectra are reported for the deuterated species of copper and silver hydroxide, 63CuOD, 107AgOD, and 109AgOD. Together with the CuOH and AgOH data previously reported, a number of harmonic force constants were determined. These constants are interpreted in terms of the balance between competing ionic and covalent interactions. The harmonic force field allowed the rz structures to be determined. Both molecules are strongly bent indicating considerable covalent character.

Microwave spectroscopic detection of HCCP in the X 3Σ− electronic state: Phospho-carbene, phospho-allene, or phosphorene?

Microwave spectrum of the HCCP radical was detected for the first time in the X 3Σ− ground electronic state using a source-modulated microwave spectrometer. In total, 24 rotational transitions of HCCP in the 90–360 GHz region, 9 rotational transitions of DCCP in the 260–360 GHz range, and 24 rotational transitions of H13C13CP between 130–360 GHz were measured. Hyperfine structure pertaining to the phosphorus and hydrogen nuclei was observed for HCCP, and in the case of H13C13CP, only for phosphorus. The corresponding hyperfine coupling constants were ascertained in addition to the rotational, centrifugal distortion, and fine structure constants by a least-squares analysis of the measured frequencies. From the hyperfine coupling constants determined, the spin density of unpaired electrons was estimated to be 76% for the phosphorus atom and 42% for the carbon adjacent to the hydrogen. The r0 structure of HCCP was established from the rotational constants of HCCP and its isotopically substituted species: r0(...

MICROWAVE SPECTROSCOPIC DETECTION OF A TRANSIENT PHOSPHORUS-BEARING MOLECULE, H3PO

The microwave spectrum of the transient phosphine oxide, H3PO, was detected in the gas phase for the first time using a source-modulated spectrometer. The H3PO molecule was generated in a free space cell by a dc glow discharge of a mixture of PH3, CO2, and H2 gases and the corresponding spectral lines for each rotational transition of H3PO formed a pattern clearly indicative of a symmetric top molecule. Isotopomers of H3PO, i.e., H3P18O and D3PO were also produced; H3P18O in the same fashion as for H3PO, and D3PO, in a mixture of D2 and CO2 gases passing over red phosphorus grains. In total, 54 spectral lines of H3PO, 55 lines of H3P18O, and 61 lines of D3PO were measured for the fine structure of rotational transitions, J=2–1 to 12–11. The rotational constant, B0, and centrifugal constants, DJ, DJK, and HKJ were ascertained by a least squares analysis of the measured frequencies for each of the species. Using the rotational constants of the three isotopic species, the following r0 structure was determine...

SUBMILLIMETER-WAVE SPECTRUM OF THE ASH2 RADICAL IN THE 2B1 GROUND ELECTRONIC STATE

The pure rotational spectrum of the AsH2 radical in its 2B1 ground electronic state was observed for the first time by microwave spectroscopy. The AsH2 radical was generated in a free-space cell by dc-glow discharge of a mixture of H2 and O2 gases over arsenic powder. Fifty-five fine and hyperfine components of six rotational transitions were measured in the frequency region of 304–374 GHz, and were analyzed by least-squares methods. Molecular constants, including the rotational constants, the centrifugal distortion constants, the spin-rotation coupling constant incorporating the centrifugal distortion term, and the hyperfine coupling constants associated with the arsenic and hydrogen nuclei, were precisely determined. The bonding in AsH2 was discussed on the basis of the hyperfine coupling constants, first determined in the present study.

Receiver Performance of the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on the International Space Station

Superconducting devices were used to make atmospheric limb observations from space for the first time. The Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) is a superconductor-insulator-superconductor (SIS) receiver in frequency bands of 625 and 650 GHz. SMILES was deployed on the International Space Station. SMILES observed atmospheric limb spectra for six months from October 2009 to April 2010. The sensitivity of the receiver is the most important performance parameter for microwave atmospheric limb observation, in which the receiver measures, sometimes very weak, thermal line emissions. The SMILES SIS receivers demonstrated limb observations with a sensitivity more than one order of magnitude better than that of conventional limb sensors. The sensitivity of the SMILES receivers in space was 315 K-322 K in a definition of single-sideband system noise temperature at the antenna; this met the instrument requirement with a large margin. The SMILES-receiver stability also met the requirement; the stability time of the receiver was 8 s (and 500 s for spectroscopic data) in a frequency resolution of about 1.1 MHz. Although the stability time is shorter than the calibration period (53 s) in operational observation, the variance increment by the drift noise is found to be insignificant. The temperature resolution for the continuum signal is estimated to be better than 0.27 K. There was no evidence that the stability of the SIS receiver was influenced by the temperature fluctuation of the 4-K cooling system, which consists of a two-stage Stirling cooler and a Joule-Thomson cycle cooler. The suppression of baseline ripples is another important performance parameter of the receiver for spectral measurement like the SMILES receivers. As a result of our design of low-standing-wave optics, we found no baseline ripple in the observed spectra of SMILES in practical level.