大质量分子云核和恒星形成活动

用国家台紫金山天文台13.7米望远镜的三谱线系统对23个有线翼特征的大质量恒星形成区进行了观测.获得了12个云核,发现其中5个具有外向流,2个有系统的速度变化,1个可能有塌缩,这些核的质量分布在9.4*10e2到2.2*10e5个太阳质量,氢分子密度从每立方厘米3.4*10e2到1.2*10e4.外向流的质量大于3.5个太阳质量,动能高于9*10e37焦耳,比低质量年轻星体附近的外向流大很多,每个核往往包含着几十个2mass源,其色指数和亮度各不相同,但最红的那个总是在IRAS源的误差椭圆内,可能就是IRAS源的对应体.     

Survey of the Star-Formation Regions Associated with Infrared Sources Observed in the <Emphasis Type="Italic">J</Emphasis> = 1−0 Line of the CO Molecule and Its Isotopes. Results of Observations Performed in the C<Superscript>18</Superscript>O(J = 1−0) Line

We present results of observations of 23 compact cores of molecular clouds associated with IRAS “ cold” infrared sources. The observations were performed in the J = 1−0 line of the C¹⁸O molecule on a 13.7-meter radio telescope of the Purple Mountain Observatory, China. The C¹⁸O (J = 1−0) line was detected in the emission of 21 objects. Column densities of the C¹⁸O and H₂ molecules towards the maximum of integral intensity of the C¹⁸O emission were estimated in the approximation of local thermodynamic equilibrium and amounted to (2.5–10.4) · 10¹⁵cm⁻² and (1.5–6.1) · 10²² cm⁻², respectively. The kinetic temperatures determined for these maxima from the CO lines vary from 14 to 45 K. For six objects, whose mapping has been almost completed, the dimensions of the C¹⁸O emission regions are estimated to range from 0.5 to 1.2 pc. The masses of these objects lie in the range of (390–1750) M_⊙ and are close to the estimates following from the virial theorem. The range of average densities of the objects is (0.3–1.4) · 10⁴ cm⁻³. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 48, No. 7, pp. 553–562, July 2005.     

Herschel and the TeraHertz sky

Herschel is a spatial submillimetre observatory with spectroscopic and imaging capabilities covering the range from 55 to 671 μm (0.44 to 5.5 THz) partly explored for the first time here. With a primary mirror of 3.5 m, it is presently the largest telescope launched. Its primary targets are the cold dust, the light hydrides, with a special focus on H₂O, and a few species of high interest like C⁺ and O₂ in both our Galaxy and other galaxies. Its main focus is on star formation in all its possible aspects including cosmological metal enrichment evolution, statistics on prestellar cores or chemistry of protostar outflow terminal shocks to name only a few. We will describe the telescope and its three instruments, a selection of general results and we will focus on one typical case in greater detail, the observation of water in massive star forming regions. Herschel was launched in May 2009 and should function 3.5 years.     

光深对大质量恒星形成团块化学性质研究的影响

本文使用文献中的N₂H⁺(1-0)、H¹³CO⁺(1-0)、HCN(1-0)和HN¹³C(1-0)谱线数据研究大质量恒星形成团块的化学性质和演化,发现H¹³CO⁺和HN¹³C的丰度受H₂柱密度的影响. 由于从A阶段到B阶段这两个丰度的中值增加了近10倍,H¹³CO⁺和HN¹³C适合追踪大质量恒星形成团块的演化. 从A到B阶段四种分子丰度增长速度从高到低依次为H¹³CO⁺、HCN、HN¹³C、N₂H⁺. 结果表明进行光学薄分子谱线的高分辨率观测对于研究大质量恒星形成团块的化学演化是必要的.     

Stark spectroscopy with the CO laser: The ν3 fundamental band of H2CO

The ν₃ fundamental band of H₂CO (CH₂ scissoring motion) has been studied by means of CO laser Stark spectroscopy and conventional infrared absorption spectroscopy. The primary aim of the work was to determine the dipole moment of H₂CO in the v₃ = 1 state, and the value determined was 2.3250 ± 0.0025 D. The spectrum was analyzed with the inclusion of the Coriolis interactions among ν₃, ν₄, and ν₆ so that “true” rotational constants were determined for ν₃; “effective” constants obtained by ignoring these interactions were also determined. The ν₃ band origin was determined to be 1500.174 ± 0.002 cm^?1. The H₂CO spectrum was also used as a means of determining the frequencies of some ¹³C¹⁶O and ¹²C¹⁸O laser lines in the 1500 cm^?1 region relative to ¹²C¹⁶O lines.     

Comparative study of the relationships between CO isotopic luminosities and infrared luminosity for the Galactic dense cores

Combining the 12CO(1-0),13CO(1-0),and C18O(1-0) data with IRAS four band data,we here estimate the physical parameters such as size,viral mass,and CO J=1-0 isotopic and infrared luminosities for 29 dense molecular clouds from two published CO samples. We further analyze the various correlations between CO J=1-0 isotopic luminosities and infrared luminosity(star formation rate,SFR) and discuss the relationships between the molecular gas tracers and SFR. The results show that 12CO(1-0),13CO(1-0) and C18O(1-0) luminosities have tight correlations with each other. CO J=1-0 isotopic luminosities and SFR show weak correlations with larger scatter than the HCN-IR correlations of 47 dense cores in the Galaxy and 65 external star-forming galaxies. This might be interpreted as that both the SFR and star formation efficiency are mainly determined by the molecular gas at high volume density rather than high column density.     

Magnetic properties of core-shell catalyst nanoparticles for carbon nanotube growth

Two types of core-shell nanoparticles have been prepared by laser pyrolysis using Fe(CO)₅ and C₂H₂ or [(CH₃)₃Si]₂O as precursors and C₂H₄ as sensitizer. The first type (about 4 nm diameter) - produced by the decomposition of Fe(CO)₅ in the presence of C₂H₄ and C₂H₂ - consists of Fe cores protected by graphenic layers. The second type (mean particle size of about 14 nm) consists also of Fe cores, yet covered by few nm thick γ-Fe₂O₃/porous polycarbosiloxane shells resulted from the [(CH₃)₃Si]₂O decomposition and superficial oxidation after air exposure. The hysteresis loops suggest a room temperature superparamagnetic behavior of the Fe-C nanopowder and a weak ferromagnetic one for larger particles in the Fe-Fe₂O₃-polymer sample. Both types of nanoparticles were finally used as a catalyst for the carbon nanotube growth by seeding Si(100) substrates via drop-casting method. CNTs were grown by Hot-Filament Direct.Current PE CVD technique from C₂H₂ and H₂ at 980 K. It is suggested that the increased density and orientation degree observed for the multiwall nanotubes grown from Fe-Fe₂O₃-polymer nanoparticles could be due to their magnetic behavior and surface composition.     

Rotational spectra of mono-substituted asymmetric C6H6-H2O dimers

This paper reports the assignment of the rotational spectra of the m = 0 and 1 states of ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers. The m = 1 progression was not identified or assigned for both ¹³CC₅H₆-H₂O and C₆H₅D-H₂O in the earlier work, though for the symmetric isotopomers (C₆H₆-H₂O/D₂O/H₂¹⁸O), they were identified [H.S. Gutowsky, T. Emilsson, E. Arunan, J. Chem. Phys. 99 (1993) 4883]. The m = 1 transitions for ¹³CC₅H₆-H₂O and C₆H₅D-H₂O were split into two, unlike that of the parent C₆H₆-H₂O isotopomer. The splitting varied, somewhat randomly, with quantum numbers J and K. The m = 0 lines of ¹³CC₅H₆-H₂O had significant overlap with the m = 1 lines of the parent isotopomer, clouding proper assignment, and leading to an rms deviation of about 200 kHz in the earlier work. The general semi-rigid molecular Hamiltonian coupled to an internal rotor, described recently by Duan et al. [Y.B. Duan, H.M. Zhang, K. Takagi, J. Chem. Phys. 104 (1996) 3914], is used in this work to assign both m = 0 and 1 states of ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers. Consequently, the m = 0 fits for ¹³CC₅H₆-H₂O/D₂O have an rms deviation of only 4/7 kHz, comparable to experimental uncertainties. The fits for m = 1 transitions for ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers have an rms deviation of about 200 kHz. However, it is of the same order of magnitude as that of the m = 1 state of the parent C₆H₆-H₂O dimer. The A rotational constants determined from the m = 0 fits for both ¹³CC₅H₆-H₂O and ¹³CC₅H₆-D₂O isotopomers are identical and very close to the C rotational constant for ¹³CC₅H₆. This provides a direct experimental determination for the C rotational constant of ¹³CC₅H₆, which has a negligible dipole moment.     

A precise study of the rotational spectrum of formaldehyde H212C16O,H213C16O,H212C18O,H213C18O

The rotational spectra of formaldehyde, H₂¹²C¹⁶O and its isotopic species H₂¹³C¹⁶O, H₂¹²C¹⁸O, and H₂¹³C¹⁸O have been investigated in the ground vibrational state in the frequency region between 8 and 460 GHz. For most cases in which measurements of the a-type R- and Q-branch transitions already existed the accuracy of the line position has been improved to about 10 kHz. For H₂¹²C¹⁶O and H₂¹³C¹⁶O a large number of ΔK_a = ±2 transitions were measured with similar accuracy. These new data when combined with all other available data and appropriate weightings lead to a set of ground state parameters which for the first time are compatible with infrared and ultraviolet data. The rotational constants (and 3σ standard deviations) obtained using Watson's A-reduced Hamiltonian are:

     

10.

IUPAC critical evaluation of the rotational-vibrational spectra of water vapor. Part II: Energy levels and transition wavenumbers for HDO, HDO, and HDO     

Jonathan Tennyson  Peter F. Bernath  Alain Campargue  Ludovic Daumont  Joseph T. Hodges  Oleg L. Polyansky  Laurence S. Rothman  Ann Carine Vandaele  Sophie Fally  Tibor Furtenbacher  Shui-Ming Hu  Boris A. Voronin 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(15):2160-1106

This is the second of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This article presents energy levels and line positions of the following singly deuterated isotopologues of water: HD¹⁶O, HD¹⁷O, and HD¹⁸O. The MARVEL (measured active rotational-vibrational energy levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0-22 708, 0-1674, and 0-12 105 cm⁻¹ for HD¹⁶O, HD¹⁷O, and HD¹⁸O, respectively. For HD¹⁶O, 54 740 transitions were analyzed from 76 sources, the lines come from spectra recorded both at room temperature and from hot samples. These lines correspond to 36 690 distinct assignments and 8818 energy levels. For HD¹⁷O, only 485 transitions could be analyzed from three sources; the lines correspond to 162 MARVEL energy levels. For HD¹⁸O, 8729 transitions were analyzed from 11 sources and these lines correspond to 1864 energy levels. The energy levels are checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators. This comparison shows that the measured transitions account for about 86% of the anticipated absorbance of HD¹⁶O at 296 K and that the transitions predicted by the MARVEL energy levels account for essentially all the remaining absorbance. The extensive list of MARVEL lines and levels obtained are given in the Supplementary Material of this article, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. In addition, the transition and energy level information for H₂¹⁷O and H₂¹⁸O, given in the first paper of this series [Tennyson, et al. J Quant Spectr Rad Transfer 2009;110:573-96], has been updated.     

11.

Microwave spectra of the ground vibrational state of formaldehyde substituted with 17O and 18O     

Danny T. Davies  Richard J. Richards  M.C.L. Gerry 《Journal of Molecular Spectroscopy》1980,80(2):307-319

Pure rotational transitions in the ground vibrational state have been measured for H₂¹²C¹⁸O, H₂¹²C¹⁷O, H₂¹³C¹⁸O, and H₂¹³C¹⁷O in the frequency region 8–75 GHz. These have included both Q- and R-branch transitions, and have permitted accurate evaluation of rotational constants and several quartic centrifugal distortion constants for each species. These in turn have permitted the prediction of several transitions of possible use in radioastronomy.     

12.

The infrared spectrum of the CO dimer     

A.R.W McKellar 《Journal of Molecular Spectroscopy》2004,226(2):190-195

The infrared spectrum of (¹²C¹⁸O)₂ has been studied for the first time using a tunable diode laser spectrometer in the 2095 cm⁻¹ region to probe a pulsed supersonic jet expansion. Very dilute gas mixtures of CO in He were used, resulting in small consumption of ¹²C¹⁸O sample gas, as well as cold and simple spectra. The results were analyzed using a term value scheme to obtain model-independent energies for 7 rotational levels belonging to 2 stacks in the lower state, v_CO=0, and 22 levels belonging to 7 stacks in the upper state, v_CO=1. The two ground state isomers of the CO dimer were found to be separated by only 0.639 cm⁻¹ for (¹²C¹⁸O)₂. These results provide a foundation for future studies of the millimeter wave spectrum.     

13.

Adsorption of CO and C₂H₄ on Rh-loaded thin-film dysprosium oxide     

D.R. Mullins 《Surface science》2006,600(13):2718-2725

A dysprosium oxide thin film was deposited on Ru(0 0 0 1) by vapor depositing Dy in 2 × 10⁻⁷ torr O₂ while the Ru was at 700 K. The film was ca. 5 nm thick and produced a p(1.4 × 1.4) LEED pattern relative to the Ru(0 0 0 1) substrate. The adsorption and reaction of CO and C₂H₄ adsorbed on Rh supported on the Dy₂O₃ film were studied by TPD and SXPS. The CO initially reacted with loosely bound oxygen in the substrate to produce CO₂. After the loosely bound oxygen was removed, the CO adsorbed non-dissociatively in a manner similar to what is seen on Rh(1 1 1). C₂H₄ adsorbed on the Rh particles and underwent progressive dehydrogenation to produce H₂ during TPD. The C from the C₂H₄ reacted with the O in Dy₂O₃ to produce CO. CO dissociation on the Rh particles could be promoted by treating the Dy₂O₃ with C₂H₄ before CO exposure.     

14.

Discovery of multiple bands of isotopic CO₂ in the prime spectral regions used when searching for CH₄ and HDO on Mars     

Geronimo L. Villanueva  Michael J. Mumma  Tilak Hewagama 《Journal of Quantitative Spectroscopy & Radiative Transfer》2008,109(6):883-894

We present new measurements of vibrational band systems of isotopic carbon dioxide (CO₂) with multiple strong lines in the wavelength region 3.3-3.7 μm. In our ground-based searches for methane (CH₄) and other biomarker gases on Mars, we discovered two new vibrational band systems that we identify as the previously unknown ν₂+ν₃ band of ¹⁶O¹²C¹⁸O and the 2ν₁ band of the rare isotope ¹⁶O¹³C¹⁸O. We also extended and provide refined spectroscopic constants for the 2ν₁ band of ¹⁶O¹²C¹⁷O, detecting 38 new lines. The newly discovered 2ν₁ band of ¹⁶O¹³C¹⁸O at 3.7 μm and the 2ν₁ band of ¹⁶O¹²C¹⁷O at 3.6 μm extend over the prime spectral region used when searching for deuterated water (HDO) and formaldehyde (H₂CO) on Mars. The ν₂+ν₃ band of ¹⁶O¹²C¹⁸O at 3.3 μm interferes with the ν₃ band of CH₄ at 3.3 μm. If unrecognized, even weak bands of CO₂ can obscure searches for trace gases on Mars, so it is important to quantify them. Here, we report molecular parameters from the measured line positions that agree well with values calculated from the known energy levels of these isotopologues, and we provide absolute band strengths for each system.     

15.

The reaction of allyl radicals with oxygen atoms—rate coefficient and product branching     

Karlheinz Hoyermann  Jörg Nothdurft  Jens Wehmeyer 《Proceedings of the Combustion Institute》2009,32(1):157-164

The primary product formation of the C₃H₅ + O reaction in the gas phase has been studied at room temperature. Allyl radicals (C₃H₅) and O atoms were generated by laser flash photolysis at λ = 193 nm of the precursors C₃H₅Cl, C₃H₅Br, C₆H₁₀ (1,5-hexadiene), and SO₂, respectively. The educts and the products were detected by using quantitative FTIR spectroscopy. The combined product analysis of the experiments with the different precursors leads to the following relative branching fractions: C₃H₅ + O → C₃H₄O + H (47%), C₂H₄ + H + CO (41%), H₂CO + C₂H₂ + H (7%), CH₃CCH + OH and CH₂CCH₂ + OH (<5%). The rate of reaction has been studied relative to CH₃OCH₂ + O and C₂H₅ + O in the temperature range from 300 to 623 K. Here, the radicals were produced via the fast reactions of propene, dimethyl ether, and ethane, respectively, with atomic fluorine. Laser-induced multiphoton ionization combined with TOF mass spectrometry and molecular beam sampling from a flow reactor was used for the specific and sensitive detection of the C₃H₅, C₂H₅, and CH₃COCH₂ radicals. The rate coefficient of the reaction C₃H₅ + O was derived with reference to the reaction C₂H₅ + O leading to k(C₃H₅ + O) = (1.11 ± 0.2) × 10¹⁴ cm³/(mol s) in the temperature range 300-623 K. The C₃H₅ + O rate and channel branching, when incorporated in a suitable detailed reaction mechanism, have a large influence on benzene and allyl concentration profiles in fuel-rich propene flames, on the propene flame speed, and on propene ignition delay times.     

16.

Microwave spectra of the ground vibrational state of formaldehyde substituted with O and O     

Danny T. Davies  Richard J. Richards  M. C. L. Gerry 《Journal of Molecular Spectroscopy》1980,80(2)

Pure rotational transitions in the ground vibrational state have been measured for H₂¹²C¹⁸O, H₂¹²C¹⁷O, H₂¹³C¹⁸O, and H₂¹³C¹⁷O in the frequency region 8–75 GHz. These have included both Q- and R-branch transitions, and have permitted accurate evaluation of rotational constants and several quartic centrifugal distortion constants for each species. These in turn have permitted the prediction of several transitions of possible use in radioastronomy.     

17.

A precise study of the rotational spectrum of formaldehyde H₂CO, H₂CO, H₂CO, H₂CO     

R. Cornet  G. Winnewisser   《Journal of Molecular Spectroscopy》1980,80(2)

The rotational spectra of formaldehyde, H₂¹²C¹⁶O and its isotopic species H₂¹³C¹⁶O, H₂¹²C¹⁸O, and H₂¹³C¹⁸O have been investigated in the ground vibrational state in the frequency region between 8 and 460 GHz. For most cases in which measurements of the a-type R- and Q-branch transitions already existed the accuracy of the line position has been improved to about 10 kHz. For H₂¹²C¹⁶O and H₂¹³C¹⁶O a large number of ΔK_a = ±2 transitions were measured with similar accuracy. These new data when combined with all other available data and appropriate weightings lead to a set of ground state parameters which for the first time are compatible with infrared and ultraviolet data. The rotational constants (and 3σ standard deviations) obtained using Watson's A-reduced Hamiltonian are:

Full-size image

     

18.

Line Shift Investigations for Different Isotopomers of Carbon Monoxide     

B. Sumpf  J.P. Burrows  A. Kissel  H.-D. Kronfeldt  O. Kurtz  I. Meusel  J. Orphal  S. Voigt 《Journal of Molecular Spectroscopy》1998,190(2):226-231

Line shift coefficients for five lines of five different isotopomers in the fundamental band of CO in the spectral region near 2058 cm⁻¹were measured using a three channel lead salt diode laser spectrometer. The study includes the linesP(3) of¹³C¹⁷O,R(3) of¹³C¹⁸O,P(9) of¹²C¹⁸O,P(10) of¹³C¹⁶O, andP(21) of¹²C¹⁶O, and covers collisions with N₂, O₂, H₂, D₂, He, Ne, Ar, Kr, and Xe. Line shifts of the isotopomers¹³C¹⁶O,¹²C¹⁸O,¹³C¹⁸O, and¹³C¹⁷O were determined for the first time. Within the experimental uncertainty no significant dependence of the shift effect on the isotopomer was found. TheR-branch line under study shows a smaller line shift coefficient than aP-branch line with a similar rotational quantum number. With increasing mass of the noble gas perturber the absolute size of the shift coefficient increases. Moreover self- and nitrogen-broadening coefficients for the isotopomer lines were determined. Compared to previous measurements no significant deviations between different isotopomers were observed.     

19.

The oxidation of H₂CO on a copper(110) surface     

Israel E. Wachs  Robert J. Madix 《Surface science》1979,84(2):375-386

The oxidation of H₂C¹⁶O by adsorbed ¹⁸O was studied on an Cu(110) sample by temperature programmed reaction spectroscopy. Formaldehyde exchanged its oxygen with surface ¹⁸O upon adsorption to yield H₂C¹⁸O_(a) and ¹⁶O_(a). Formaldehyde was also oxidized by surface ¹⁶O and ¹⁸O atoms to H₂COO which subsequently released one of the hydrogen atoms to form HCOO. The evolution of H₂ from the Cu(110) surface was desorption limited, and the low pre-exponential factor for the recombination of the surface hydrogen atoms suggested stringent requirement on the trajectories of the colliding partners. The formate was very stable and dissociated at elevated temperatures to simultaneously yield H₂ and CO₂. The surface concentration of ¹⁸O exerted a pronounced affect on the activity of the oxidation of formaldehyde on Cu(110).     

20.

Diode-laser measurements and calculations of CO 1-0 P(4) line broadening in the 294- to 765-K temperature range     

《Journal of Quantitative Spectroscopy & Radiative Transfer》1986,35(5):357-363

We present first diode-laser measurements of C¹²O¹⁶ 1-0 P(4) line broadening by Ar, N₂ and H₂O at high temperatures, together with the line-intensity value at 300 K. A T^-β dependence of line-widths on temperature is deduced from measurements in the 294- to 765-K and 0.2- to 1.2- atm ranges (β = 0.69±0.02, β = 0.69±0.02, β = 0.59±0.05 for Ar, N₂ and H₂O broadening, respectively). Calculations for CO-Ar and CO-N₂ with the model proposed by Robert and Bonamy give very satisfactory results.     

	H212C16O	H213C16O	H212C18O	H213C18O
A/MHz	281 970.572 (24)	281 993.258(135)	281 961.94 (39)	281 985.00 (93)
B/MHz	38 836.0456(13)	37 811.0887(25)	36 904.1693(66)	35 859.256(10)
C/MHz	34 002.2034(12)	33 213.9790(25)	32 511.5311(63)	31 697.868(10)

IUPAC critical evaluation of the rotational-vibrational spectra of water vapor. Part II: Energy levels and transition wavenumbers for HDO, HDO, and HDO

This is the second of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This article presents energy levels and line positions of the following singly deuterated isotopologues of water: HD¹⁶O, HD¹⁷O, and HD¹⁸O. The MARVEL (measured active rotational-vibrational energy levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0-22 708, 0-1674, and 0-12 105 cm⁻¹ for HD¹⁶O, HD¹⁷O, and HD¹⁸O, respectively. For HD¹⁶O, 54 740 transitions were analyzed from 76 sources, the lines come from spectra recorded both at room temperature and from hot samples. These lines correspond to 36 690 distinct assignments and 8818 energy levels. For HD¹⁷O, only 485 transitions could be analyzed from three sources; the lines correspond to 162 MARVEL energy levels. For HD¹⁸O, 8729 transitions were analyzed from 11 sources and these lines correspond to 1864 energy levels. The energy levels are checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators. This comparison shows that the measured transitions account for about 86% of the anticipated absorbance of HD¹⁶O at 296 K and that the transitions predicted by the MARVEL energy levels account for essentially all the remaining absorbance. The extensive list of MARVEL lines and levels obtained are given in the Supplementary Material of this article, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. In addition, the transition and energy level information for H₂¹⁷O and H₂¹⁸O, given in the first paper of this series [Tennyson, et al. J Quant Spectr Rad Transfer 2009;110:573-96], has been updated.     

Microwave spectra of the ground vibrational state of formaldehyde substituted with 17O and 18O

Pure rotational transitions in the ground vibrational state have been measured for H₂¹²C¹⁸O, H₂¹²C¹⁷O, H₂¹³C¹⁸O, and H₂¹³C¹⁷O in the frequency region 8–75 GHz. These have included both Q- and R-branch transitions, and have permitted accurate evaluation of rotational constants and several quartic centrifugal distortion constants for each species. These in turn have permitted the prediction of several transitions of possible use in radioastronomy.     

The infrared spectrum of the CO dimer

The infrared spectrum of (¹²C¹⁸O)₂ has been studied for the first time using a tunable diode laser spectrometer in the 2095 cm⁻¹ region to probe a pulsed supersonic jet expansion. Very dilute gas mixtures of CO in He were used, resulting in small consumption of ¹²C¹⁸O sample gas, as well as cold and simple spectra. The results were analyzed using a term value scheme to obtain model-independent energies for 7 rotational levels belonging to 2 stacks in the lower state, v_CO=0, and 22 levels belonging to 7 stacks in the upper state, v_CO=1. The two ground state isomers of the CO dimer were found to be separated by only 0.639 cm⁻¹ for (¹²C¹⁸O)₂. These results provide a foundation for future studies of the millimeter wave spectrum.     

Adsorption of CO and C2H4 on Rh-loaded thin-film dysprosium oxide

A dysprosium oxide thin film was deposited on Ru(0 0 0 1) by vapor depositing Dy in 2 × 10⁻⁷ torr O₂ while the Ru was at 700 K. The film was ca. 5 nm thick and produced a p(1.4 × 1.4) LEED pattern relative to the Ru(0 0 0 1) substrate. The adsorption and reaction of CO and C₂H₄ adsorbed on Rh supported on the Dy₂O₃ film were studied by TPD and SXPS. The CO initially reacted with loosely bound oxygen in the substrate to produce CO₂. After the loosely bound oxygen was removed, the CO adsorbed non-dissociatively in a manner similar to what is seen on Rh(1 1 1). C₂H₄ adsorbed on the Rh particles and underwent progressive dehydrogenation to produce H₂ during TPD. The C from the C₂H₄ reacted with the O in Dy₂O₃ to produce CO. CO dissociation on the Rh particles could be promoted by treating the Dy₂O₃ with C₂H₄ before CO exposure.     

Discovery of multiple bands of isotopic CO2 in the prime spectral regions used when searching for CH4 and HDO on Mars

We present new measurements of vibrational band systems of isotopic carbon dioxide (CO₂) with multiple strong lines in the wavelength region 3.3-3.7 μm. In our ground-based searches for methane (CH₄) and other biomarker gases on Mars, we discovered two new vibrational band systems that we identify as the previously unknown ν₂+ν₃ band of ¹⁶O¹²C¹⁸O and the 2ν₁ band of the rare isotope ¹⁶O¹³C¹⁸O. We also extended and provide refined spectroscopic constants for the 2ν₁ band of ¹⁶O¹²C¹⁷O, detecting 38 new lines. The newly discovered 2ν₁ band of ¹⁶O¹³C¹⁸O at 3.7 μm and the 2ν₁ band of ¹⁶O¹²C¹⁷O at 3.6 μm extend over the prime spectral region used when searching for deuterated water (HDO) and formaldehyde (H₂CO) on Mars. The ν₂+ν₃ band of ¹⁶O¹²C¹⁸O at 3.3 μm interferes with the ν₃ band of CH₄ at 3.3 μm. If unrecognized, even weak bands of CO₂ can obscure searches for trace gases on Mars, so it is important to quantify them. Here, we report molecular parameters from the measured line positions that agree well with values calculated from the known energy levels of these isotopologues, and we provide absolute band strengths for each system.     

The reaction of allyl radicals with oxygen atoms—rate coefficient and product branching

The primary product formation of the C₃H₅ + O reaction in the gas phase has been studied at room temperature. Allyl radicals (C₃H₅) and O atoms were generated by laser flash photolysis at λ = 193 nm of the precursors C₃H₅Cl, C₃H₅Br, C₆H₁₀ (1,5-hexadiene), and SO₂, respectively. The educts and the products were detected by using quantitative FTIR spectroscopy. The combined product analysis of the experiments with the different precursors leads to the following relative branching fractions: C₃H₅ + O → C₃H₄O + H (47%), C₂H₄ + H + CO (41%), H₂CO + C₂H₂ + H (7%), CH₃CCH + OH and CH₂CCH₂ + OH (<5%). The rate of reaction has been studied relative to CH₃OCH₂ + O and C₂H₅ + O in the temperature range from 300 to 623 K. Here, the radicals were produced via the fast reactions of propene, dimethyl ether, and ethane, respectively, with atomic fluorine. Laser-induced multiphoton ionization combined with TOF mass spectrometry and molecular beam sampling from a flow reactor was used for the specific and sensitive detection of the C₃H₅, C₂H₅, and CH₃COCH₂ radicals. The rate coefficient of the reaction C₃H₅ + O was derived with reference to the reaction C₂H₅ + O leading to k(C₃H₅ + O) = (1.11 ± 0.2) × 10¹⁴ cm³/(mol s) in the temperature range 300-623 K. The C₃H₅ + O rate and channel branching, when incorporated in a suitable detailed reaction mechanism, have a large influence on benzene and allyl concentration profiles in fuel-rich propene flames, on the propene flame speed, and on propene ignition delay times.     

Microwave spectra of the ground vibrational state of formaldehyde substituted with O and O

Pure rotational transitions in the ground vibrational state have been measured for H₂¹²C¹⁸O, H₂¹²C¹⁷O, H₂¹³C¹⁸O, and H₂¹³C¹⁷O in the frequency region 8–75 GHz. These have included both Q- and R-branch transitions, and have permitted accurate evaluation of rotational constants and several quartic centrifugal distortion constants for each species. These in turn have permitted the prediction of several transitions of possible use in radioastronomy.     

A precise study of the rotational spectrum of formaldehyde H2CO, H2CO, H2CO, H2CO

The rotational spectra of formaldehyde, H₂¹²C¹⁶O and its isotopic species H₂¹³C¹⁶O, H₂¹²C¹⁸O, and H₂¹³C¹⁸O have been investigated in the ground vibrational state in the frequency region between 8 and 460 GHz. For most cases in which measurements of the a-type R- and Q-branch transitions already existed the accuracy of the line position has been improved to about 10 kHz. For H₂¹²C¹⁶O and H₂¹³C¹⁶O a large number of ΔK_a = ±2 transitions were measured with similar accuracy. These new data when combined with all other available data and appropriate weightings lead to a set of ground state parameters which for the first time are compatible with infrared and ultraviolet data. The rotational constants (and 3σ standard deviations) obtained using Watson's A-reduced Hamiltonian are:

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Line Shift Investigations for Different Isotopomers of Carbon Monoxide

Line shift coefficients for five lines of five different isotopomers in the fundamental band of CO in the spectral region near 2058 cm⁻¹were measured using a three channel lead salt diode laser spectrometer. The study includes the linesP(3) of¹³C¹⁷O,R(3) of¹³C¹⁸O,P(9) of¹²C¹⁸O,P(10) of¹³C¹⁶O, andP(21) of¹²C¹⁶O, and covers collisions with N₂, O₂, H₂, D₂, He, Ne, Ar, Kr, and Xe. Line shifts of the isotopomers¹³C¹⁶O,¹²C¹⁸O,¹³C¹⁸O, and¹³C¹⁷O were determined for the first time. Within the experimental uncertainty no significant dependence of the shift effect on the isotopomer was found. TheR-branch line under study shows a smaller line shift coefficient than aP-branch line with a similar rotational quantum number. With increasing mass of the noble gas perturber the absolute size of the shift coefficient increases. Moreover self- and nitrogen-broadening coefficients for the isotopomer lines were determined. Compared to previous measurements no significant deviations between different isotopomers were observed.     

The oxidation of H2CO on a copper(110) surface

The oxidation of H₂C¹⁶O by adsorbed ¹⁸O was studied on an Cu(110) sample by temperature programmed reaction spectroscopy. Formaldehyde exchanged its oxygen with surface ¹⁸O upon adsorption to yield H₂C¹⁸O_(a) and ¹⁶O_(a). Formaldehyde was also oxidized by surface ¹⁶O and ¹⁸O atoms to H₂COO which subsequently released one of the hydrogen atoms to form HCOO. The evolution of H₂ from the Cu(110) surface was desorption limited, and the low pre-exponential factor for the recombination of the surface hydrogen atoms suggested stringent requirement on the trajectories of the colliding partners. The formate was very stable and dissociated at elevated temperatures to simultaneously yield H₂ and CO₂. The surface concentration of ¹⁸O exerted a pronounced affect on the activity of the oxidation of formaldehyde on Cu(110).     

Diode-laser measurements and calculations of CO 1-0 P(4) line broadening in the 294- to 765-K temperature range

We present first diode-laser measurements of C¹²O¹⁶ 1-0 P(4) line broadening by Ar, N₂ and H₂O at high temperatures, together with the line-intensity value at 300 K. A T^-β dependence of line-widths on temperature is deduced from measurements in the 294- to 765-K and 0.2- to 1.2- atm ranges (β = 0.69±0.02, β = 0.69±0.02, β = 0.59±0.05 for Ar, N₂ and H₂O broadening, respectively). Calculations for CO-Ar and CO-N₂ with the model proposed by Robert and Bonamy give very satisfactory results.