Highly Accurate Potential Energy Surface, Dipole Moment Surface, Rovibrational Energy Levels, and Infrared Line List for (32)S(16)O2 up to 8000 cm(exp -1)

NASA Technical Reports Server (NTRS)

Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

2014-01-01

A purely ab initio potential energy surface (PES) was refined with selected (32)S(16)O2 HITRAN data. Compared to HITRAN, the root-mean-squares error (RMS) error for all J=0-80 rovibrational energy levels computed on the refined PES (denoted Ames-1) is 0.013 cm(exp -1). Combined with a CCSD(T)/aug-cc-pV(Q+d)Z dipole moment surface (DMS), an infrared (IR) line list (denoted Ames-296K) has been computed at 296K and covers up to 8,000 cm(exp -1). Compared to the HITRAN and CDMS databases, the intensity agreement for most vibrational bands is better than 85-90%. Our predictions for (34)S(16)O2 band origins, higher energy (32)S(16)O2 band origins and missing (32)S(16)O2 IR bands have been verified by most recent experiments and available HITRAN data. We conclude that the Ames-1 PES is able to predict (32/34)S(16)O2 band origins below 5500 cm(exp -1) with 0.01-0.03 cm(exp -1) uncertainties, and the Ames-296K line list provides continuous, reliable and accurate IR simulations. The Ka-dependence of both line position and line intensity errors is discussed. The line list will greatly facilitate SO2 IR spectral experimental analysis, as well as elimination of SO2 lines in high-resolution astronomical observations.

Full-dimensional Quantum Calculations of Rovibrational Transitions in CS induced by H2

NASA Astrophysics Data System (ADS)

Yang, Benhui; Zhang, Peng; Stancil, Phillip; Bowman, J.; Balakrishnan, N.; Forrey, R.

2017-04-01

Carbon monosulfide (CS), the sulfur analogue of carbon monoxide, has been widely observed in a variety interstellar regions. An accurate prediction of its abundance requires collisional rate coefficients with ambient gases. However, the collisional rate coefficients are largely unknown and primarily rely on theoretical scattering calculations. In interstellar clouds, the dominant collision partner is H2. Rate coefficient data on CS-H2 collisions are limited to pure rotational transitions and no data exist for rovibrational transitions. In this work we evaluate the first full-dimensional potential energy surface for the CS-H2 system using high-level electronic structure theory and perform explicit quantum close-coupling calculations of rovibrational transitions in CS induced by H2 collisions. Cross sections and rate coefficients for rotational transitions are compared with previous theoretical results obtained within a rigid-rotor model. For rovibrational transitions, state-to-state rate coefficients are evaluated for several low-lying rotational levels in the first excited vibrational level of CS. Results are presented for both para-H2 and ortho-H2 collision partners. Work at UGA and Emory are supported by NASA Grant No. NNX16AF09G, at UNLV by NSF Grant No. PHY-1505557, and at Penn State by NSF Grant No. PHY-1503615.

Rovibrationally-Resolved Direct Photodissociation Through The Lyman And Werner Transitions Of H_{2}

NASA Astrophysics Data System (ADS)

Gay, Christopher; Stancil, P. C.

2008-03-01

Direct photodissociation cross sections have been obtained for the Lyman and Werner transitions of H2 using a combination of ab initio and experimentally derived potential curves and dipole transition moments. The partial cross sections have been evaluated for transitions from all 301 rovibrational levels (v'',J'') of the ground electronic state and over a wavelength range that extends from 10nm to the dissociation threshold for each particular rovibrational state. For UV-irradiated molecular gas with column densities of 1016-1019cm-2, direct photodissociation can compete with the Solomon process as an H2 destruction process. This research was supported by NASA grant NNG06GJ11G from the Astrophysics Theory Program.

Line mixing effects in isotropic Raman spectra of pure N{sub 2}: A classical trajectory study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanov, Sergey V., E-mail: serg.vict.ivanov@gmail.com; Boulet, Christian; Buzykin, Oleg G.

2014-11-14

Line mixing effects in the Q branch of pure N{sub 2} isotropic Raman scattering are studied at room temperature using a classical trajectory method. It is the first study using an extended modified version of Gordon's classical theory of impact broadening and shift of rovibrational lines. The whole relaxation matrix is calculated using an exact 3D classical trajectory method for binary collisions of rigid N{sub 2} molecules employing the most up-to-date intermolecular potential energy surface (PES). A simple symmetrizing procedure is employed to improve off-diagonal cross-sections to make them obeying exactly the principle of detailed balance. The adequacy of themore » results is confirmed by the sum rule. The comparison is made with available experimental data as well as with benchmark fully quantum close coupling [F. Thibault, C. Boulet, and Q. Ma, J. Chem. Phys. 140, 044303 (2014)] and refined semi-classical Robert-Bonamy [C. Boulet, Q. Ma, and F. Thibault, J. Chem. Phys. 140, 084310 (2014)] results. All calculations (classical, quantum, and semi-classical) were made using the same PES. The agreement between classical and quantum relaxation matrices is excellent, opening the way to the analysis of more complex molecular systems.« less

Rovibrational states of interstitial H2 in Si

NASA Astrophysics Data System (ADS)

Koch, S.; Lavrov, E. V.; Weber, J.

2011-06-01

Rovibrational Q(J) transitions of the interstitial H2 molecule in Si have been investigated by Raman scattering in the temperature range 90-388 K. In accordance with an earlier suggestion [M. Hiller, E. V. Lavrov, and J. Weber, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.74.235214 74, 235214 (2006)], it is shown that the Q(2) transition of para hydrogen couples to the TAX phonon of Si and appears in the Raman spectra at temperatures above 200 K. The results presented also indicate that the rotational J=3 state of ortho hydrogen is resonantly coupled to the OΓ phonon.

Precise ro-vibrational analysis of molecular bands forbidden in absorption: The ν8 +ν10 band of the 12C2H4 molecule

NASA Astrophysics Data System (ADS)

Ulenikov, O. N.; Gromova, O. V.; Bekhtereva, E. S.; Kashirina, N. V.; Bauerecker, S.; Horneman, V.-M.

2015-07-01

The highly accurate (experimental accuracy in line positions ∼ (1 - 2) ×10-4 cm-1) ro-vibrational spectrum of the ν8 +ν10 band of the 12C2H4 molecule was recorded for the first time with high resolution Fourier transform spectrometry and analyzed in the region of 1650-1950 cm-1 using the Hamiltonian model which takes into account Coriolis resonance interactions between the studied ν8 +ν10 band, which is forbidden in absorption, and the bands ν4 +ν8 and ν7 +ν8 . About 1570 transitions belonging to the ν8 +ν10 band were assigned in the experimental spectra with the maximum values of quantum numbers Jmax. = 35 and Kamax . = 18 . On that basis, a set of 38 vibrational, rotational, centrifugal distortion, and resonance interaction parameters was obtained from the fit. They reproduce values of 598 initial "experimental" ro-vibrational energy levels (positions of about 1570 experimentally recorded and assigned transitions) with the rms error drms = 0.00045 cm-1 (drms = 0.00028 cm-1 when upper ro-vibrational energies obtained from blended and very weak transitions were deleted from the fit).

Ab initio study of the CO-N2 complex: a new highly accurate intermolecular potential energy surface and rovibrational spectrum.

PubMed

Cybulski, Hubert; Henriksen, Christian; Dawes, Richard; Wang, Xiao-Gang; Bora, Neha; Avila, Gustavo; Carrington, Tucker; Fernández, Berta

2018-05-09

A new, highly accurate ab initio ground-state intermolecular potential-energy surface (IPES) for the CO-N2 complex is presented. Thousands of interaction energies calculated with the CCSD(T) method and Dunning's aug-cc-pVQZ basis set extended with midbond functions were fitted to an analytical function. The global minimum of the potential is characterized by an almost T-shaped structure and has an energy of -118.2 cm-1. The symmetry-adapted Lanczos algorithm was used to compute rovibrational energies (up to J = 20) on the new IPES. The RMSE with respect to experiment was found to be on the order of 0.038 cm-1 which confirms the very high accuracy of the potential. This level of agreement is among the best reported in the literature for weakly bound systems and considerably improves on those of previously published potentials.

A Solar-Pumped Fluorescence Model for Line-By-Line Emission Intensities in the B-X, A-X, and X-X Band Systems of 12C14N

NASA Technical Reports Server (NTRS)

Paganini, L.; Mumma, M. J.

2016-01-01

We present a new quantitative model for detailed solar-pumped fluorescent emission of the main isotopologue of CN. The derived fluorescence efficiencies permit estimation and interpretation of ro-vibrational infrared line intensities of CN in exospheres exposed to solar (or stellar) radiation. Our g-factors are applicable to astronomical observations of CN extending from infrared to optical wavelengths, and we compare them with previous calculations in the literature. The new model enables extraction of rotational temperature, column abundance, and production rate from astronomical observations of CN in the inner coma of comets. Our model accounts for excitation and de-excitation of rotational levels in the ground vibrational state by collisions, solar excitation to the A(sup 2)Pi(sub I) and B(sup 2)Sum(sup +) electronically excited states followed by cascade to ro-vibrational levels of X(sup 2)Sum(sup +), and direct solar infrared pumping of ro-vibrational levels in the X(sup 2)Sum(sup +) state. The model uses advanced solar spectra acquired at high spectral resolution at the relevant infrared and optical wavelengths and considers the heliocentric radial velocity of the comet (the Swings effect) when assessing the exciting solar flux for a given transition. We present model predictions for the variation of fluorescence rates with rotational temperature and heliocentric radial velocity. Furthermore, we test our fluorescence model by comparing predicted and measured line-by-line intensities for X(sup 2)Sum(sup +) (1-0) in comet C/2014 Q2 (Lovejoy), thereby identifying multiple emission lines observed at IR wavelengths.

Sub-Doppler Rovibrational Spectroscopy of the H_3^+ Cation and Isotopologues

NASA Astrophysics Data System (ADS)

Markus, Charles R.; McCollum, Jefferson E.; Dieter, Thomas S.; Kocheril, Philip A.; McCall, Benjamin J.

2017-06-01

Molecular ions play a central role in the chemistry of the interstellar medium (ISM) and act as benchmarks for state of the art ab initio theory. The molecular ion H_3^+ initiates a chain of ion-neutral reactions which drives chemistry in the ISM, and observing it either directly or indirectly through its isotopologues is valuable for understanding interstellar chemistry. Improving the accuracy of laboratory measurements will assist future astronomical observations. H_3^+ is also one of a few systems whose rovibrational transitions can be predicted to spectroscopic accuracy (<1 cm^{-1}), and with careful treatment of adiabatic, nonadiabatic, and quantum electrodynamic corrections to the potential energy surface, predictions of low lying rovibrational states can rival the uncertainty of experimental measurements New experimental data will be needed to benchmark future treatment of these corrections. Previously we have reported 26 transitions within the fundamental band of H_3^+ with MHz-level uncertainties. With recent improvements to our overall sensitivity, we have expanded this survey to include additional transitions within the fundamental band and the first hot band. These new data will ultimately be used to predict ground state rovibrational energy levels through combination differences which will act as benchmarks for ab initio theory and predict forbidden rotational transitions of H_3^+. We will also discuss progress in measuring rovibrational transitions of the isotopologues H_2D^+ and D_2H^+, which will be used to assist in future THz astronomical observations. New experimental data will be needed to benchmark future treatment of these corrections. J. N. Hodges, A. J. Perry, P. A. Jenkins II, B. M. Siller, and B. J. McCall, J. Chem. Phys. (2013), 139, 164201. A. J. Perry, J. N. Hodges, C. R. Markus, G. S. Kocheril, and B. J. McCall, J. Mol. Spectrosc. (2015), 317, 71-73. A. J. Perry, C. R. Markus, J. N. Hodges, G. S. Kocheril, and B. J. McCall, 71st

Ab Initio Effective Rovibrational Hamiltonians for Non-Rigid Molecules via Curvilinear VMP2

NASA Astrophysics Data System (ADS)

Changala, Bryan; Baraban, Joshua H.

2017-06-01

Accurate predictions of spectroscopic constants for non-rigid molecules are particularly challenging for ab initio theory. For all but the smallest systems, ``brute force'' diagonalization of the full rovibrational Hamiltonian is computationally prohibitive, leaving us at the mercy of perturbative approaches. However, standard perturbative techniques, such as second order vibrational perturbation theory (VPT2), are based on the approximation that a molecule makes small amplitude vibrations about a well defined equilibrium structure. Such assumptions are physically inappropriate for non-rigid systems. In this talk, we will describe extensions to curvilinear vibrational Møller-Plesset perturbation theory (VMP2) that account for rotational and rovibrational effects in the molecular Hamiltonian. Through several examples, we will show that this approach provides predictions to nearly microwave accuracy of molecular constants including rotational and centrifugal distortion parameters, Coriolis coupling constants, and anharmonic vibrational and tunneling frequencies.

Rovibrational Analysis of ν 2 and 2ν 5 Bands of DCOOH by High Resolution FTIR Spectroscopy

NASA Astrophysics Data System (ADS)

Tan, T. L.; Goh, K. L.; Ong, P. P.; Teo, H. H.

1999-12-01

The infrared absorption spectrum of the ν2 band of deuterated formic acid (DCOOH) was recorded using a Bomem DA3.002 Fourier transform spectrometer in the wavenumber region 2130-2300 cm-1 with an apodized resolution of 0.004 cm-1. A total of 1024 transitions were assigned to this band which is hybrid type A and B, centered at 2219.6896 ± 0.0002 cm-1. As expected, the ν2 band is coupled to 2ν5 by a c-type Coriolis interaction. Both perturbed and unperturbed transitions were assigned and fitted to give seven rovibrational constants for the ν2 = 1 state with a standard deviation of 0.00094 cm-1 using Watson's A-reduced Hamiltonian in the Ir representation. A c-type Coriolis interaction term between ν2 and 2ν5 was derived from the rovibrational analysis. The ratio of the transition moments, ‖μb/μa‖, was found to be 1.42 ± 0.10 for the hybrid band.

Collision induced broadening of ν1 band and ground state spectral lines of sulfur dioxide perturbed by N2 and O2

NASA Astrophysics Data System (ADS)

Ceselin, Giorgia; Tasinato, Nicola; Puzzarini, Cristina; Charmet, Andrea Pietropolli; Stoppa, Paolo; Giorgianni, Santi

2017-09-01

To monitor the constituents and trace pollutants of Earth atmosphere and understand its evolution, accurate spectroscopic parameters are fundamental information. SO2 is produced by both natural and anthropogenic sources and it is one of the principal causes of acid rains as well as an important component of fine aerosol particles, once oxidized to sulfate. The present work aims at determining SO2 broadening parameters using N2 and O2 as atmospherically relevant damping gases. Measurements are carried out in the infrared (IR) and mm-/sub-mm wave regions, around 8.8 μm and in the 104 GHz-1.1 THz interval, respectively. IR ro-vibrational transitions are recorded by using a tunable diode laser spectrometer, whereas the microwave spectra are recorded by using a frequency-modulated millimeter-/submillimeter-wave spectrometer. SO2-N2 and SO2-O2 collisional cross sections are retrieved for several ν1 band ro-vibrational transitions of 32S16O2, for some transitions belonging to either ν1 + ν2 - ν2 of 32S16O2 or ν1 of 34S16O2 as well as for about 20 pure rotational transitions in the vibrational ground state of the main isotopic species. From N2- and O2- broadening coefficients the broadening parameters of SO2 in air are derived. The work is completed with the study of the dependence of foreign broadening coefficients on the rotational quantum numbers.

Precise predictions of H2O line shapes over a wide pressure range using simulations corrected by a single measurement

NASA Astrophysics Data System (ADS)

Ngo, N. H.; Nguyen, H. T.; Tran, H.

2018-03-01

In this work, we show that precise predictions of the shapes of H2O rovibrational lines broadened by N2, over a wide pressure range, can be made using simulations corrected by a single measurement. For that, we use the partially-correlated speed-dependent Keilson-Storer (pcsdKS) model whose parameters are deduced from molecular dynamics simulations and semi-classical calculations. This model takes into account the collision-induced velocity-changes effects, the speed dependences of the collisional line width and shift as well as the correlation between velocity and internal-state changes. For each considered transition, the model is corrected by using a parameter deduced from its broadening coefficient measured for a single pressure. The corrected-pcsdKS model is then used to simulate spectra for a wide pressure range. Direct comparisons of the corrected-pcsdKS calculated and measured spectra of 5 rovibrational lines of H2O for various pressures, from 0.1 to 1.2 atm, show very good agreements. Their maximum differences are in most cases well below 1%, much smaller than residuals obtained when fitting the measurements with the Voigt line shape. This shows that the present procedure can be used to predict H2O line shapes for various pressure conditions and thus the simulated spectra can be used to deduce the refined line-shape parameters to complete spectroscopic databases, in the absence of relevant experimental values.

ExoMol molecular line lists - XXVII: spectra of C2H4

NASA Astrophysics Data System (ADS)

Mant, Barry P.; Yachmenev, Andrey; Yurchenko, Jonathan Tennyson Sergei N.

2018-05-01

A new line list for ethylene, 12C21H4 is presented. The line list is based on high level ab initiopotential energy and dipole moment surfaces. The potential energy surface is refined by fitting to experimental energies. The line list covers the range up to 7000 cm-1(1.43 μm) with all ro-vibrational transitions (50 billion) with the lower state below 5000 cm-1included and thus should be applicable for temperatures up to 700 K. A technique for computing molecular opacities from vibrational band intensities is proposed and used to provide temperature dependent cross sections of ethylene for shorter wavelength and higher temperatures. When combined with realistic band profiles (such as the proposed three-band model), the vibrational intensity technique offers a cheap but reasonably accurate alternative to the full ro-vibrational calculations at high temperatures and should be reliable for representing molecular opacities. The C2H4 line list, which is called MaYTY, is rmade available in electronic form from the CDS (http://cdsarc.u-strasbg.fr) and ExoMol (www.exomol.com) databases.

Temperature-dependence laws of absorption line shape parameters of the CO2 ν3 band

NASA Astrophysics Data System (ADS)

Wilzewski, J. S.; Birk, M.; Loos, J.; Wagner, G.

2018-02-01

To improve the understanding of temperature-dependence laws of spectral line shape parameters, spectra of the ν3 rovibrational band of CO2 perturbed by 10, 30, 100, 300 and 1000 mbar of N2 were recorded at nine temperatures between 190 K and 330 K using a 22 cm long single-pass absorption cell in a Bruker IFS125 HR Fourier Transform spectrometer. The spectra were fitted employing a quadratic speed-dependent hard collision model in the Hartmann-Tran implementation extended to account for line mixing in the Rosenkranz approximation by means of a multispectrum fitting approach developed at DLR. This enables high accuracy parameter retrievals to reproduce the spectra down to noise level and we present the behavior of line widths, shifts, speed-dependence-, collisional narrowing- and line mixing-parameters over this 140 K temperature range.

Raman investigation of ro-vibrational modes of interstitial H2 in Si

NASA Astrophysics Data System (ADS)

Koch, S. G.; Lavrov, E. V.; Weber, J.

2012-08-01

A Raman scattering study of ro-vibrational transitions Q(J) of the interstitial H2 in Si is presented. It is shown that the Q(2) mode of para hydrogen is coupled to the TAX phonon of Si. The mode appears in the spectra at temperatures above 200 K. The results presented also suggest that the Q(3) transition of ortho hydrogen is resonantly coupled to the OΓ phonon.

Fine-structure-resolution for Rovibrational Excitation of CN Due to H2

NASA Astrophysics Data System (ADS)

Byrd, Nat; Yang, Benhui H.; Stancil, Phillip C.

2018-06-01

Diatomic molecules can be readily excited in interstellar environments exposed to intense UV radiation, such as the inner rim of a protoplanetary disk. Non-thermal populations of excited rovibrational levels can result, for example, following decay from electronically excited states to the electronic ground state. Competition between radiative decay and collisional processes, mostly due to H2, determine the resulting rovibrational emission spectrum. For CN, and other open-shell molecules, the resulting spectrum will be complicated due to fine-structure splitting of the rotational levels. In some cases, fine-structure resolution has been previously computed for rotational transitions in atom- or diatom-diatom collisional processes. Here we present the first fine-structure resolution for vibrational deexcitation for CN colliding with H2. The collisional cross sections were computed using a 6D potential energy surface with a full close-coupling approach. Fine-structure resolution is obtained by adopting an angular momentum recoupling scheme to transform the scattering matrices to a recoupled basis. Here we present low-energy calculations for the v=1 to 0 transition.This work was supported by NASA Grant NNX16AF09G.

Rovibrational constants of the ground state and v8 = 1 state of 13C2HD3 by high-resolution FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Ng, L. L.; Tan, T. L.

2016-06-01

The Fourier transform infrared (FTIR) spectrum of the c-type ν8 band of 13C2HD3 was recorded for the first time at a unapodized resolution of 0.0063 cm-1 in the wavenumber region of 830-1000 cm-1. Through the fitting of a total of 1057 assigned infrared transitions using Watson's A-reduced Hamiltonian in the Ir representation, rovibrational constants for the upper state (v8 = 1) up to five quartic centrifugal distortion terms were derived for the first time with a root-mean-square (rms) deviation of 0.00073 cm-1. The band center of ν8 of 13C2HD3 was found to be 913.011021(55) cm-1. Ground state rovibrational constants up to five quartic terms of 13C2HD3 were also determined from a fit of 453 ground state combination-differences from the present infrared measurements with an rms deviation of 0.00072 cm-1 for the first time. The uncertainty of the measured infrared lines was estimated to be ±0.0012 cm-1. From the ground state rotational constants, the inertial defect of 13C2HD3 was calculated to be 0.06973(16) uÅ2, showing the high planarity of the molecule.

Highly accurate potential energy surface, dipole moment surface, rovibrational energy levels, and infrared line list for {sup 32}S{sup 16}O{sub 2} up to 8000 cm{sup −1}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Xinchuan, E-mail: Xinchuan.Huang-1@nasa.gov, E-mail: Timothy.J.Lee@nasa.gov; Schwenke, David W., E-mail: David.W.Schwenke@nasa.gov; Lee, Timothy J., E-mail: Xinchuan.Huang-1@nasa.gov, E-mail: Timothy.J.Lee@nasa.gov

2014-03-21

A purely ab initio potential energy surface (PES) was refined with selected {sup 32}S{sup 16}O{sub 2} HITRAN data. Compared to HITRAN, the root-mean-squares error (σ{sub RMS}) for all J = 0–80 rovibrational energy levels computed on the refined PES (denoted Ames-1) is 0.013 cm{sup −1}. Combined with a CCSD(T)/aug-cc-pV(Q+d)Z dipole moment surface (DMS), an infrared (IR) line list (denoted Ames-296K) has been computed at 296 K and covers up to 8000 cm{sup −1}. Compared to the HITRAN and CDMS databases, the intensity agreement for most vibrational bands is better than 85%–90%. Our predictions for {sup 34}S{sup 16}O{sub 2} band origins,more » higher energy {sup 32}S{sup 16}O{sub 2} band origins and missing {sup 32}S{sup 16}O{sub 2} IR bands have been verified by most recent experiments and available HITRAN data. We conclude that the Ames-1 PES is able to predict {sup 32/34}S{sup 16}O{sub 2} band origins below 5500 cm{sup −1} with 0.01–0.03 cm{sup −1} uncertainties, and the Ames-296K line list provides continuous, reliable and accurate IR simulations. The K{sub a}-dependence of both line position and line intensity errors is discussed. The line list will greatly facilitate SO{sub 2} IR spectral experimental analysis, as well as elimination of SO{sub 2} lines in high-resolution astronomical observations.« less

Rovibrational transitions of H2 by collision with H+ at high temperature

NASA Astrophysics Data System (ADS)

González-Lezana, T.; Honvault, P.

2017-05-01

The H+ + H2 reaction is studied by means of both exact and statistical quantum methods. Integral cross-sections for processes initiated with rotationally excited H2(v, j = 1) to produce molecular hydrogen in its rotational ground state are reported up to a value of the collision energy of 3 eV. Rate constants for state-to-state transitions between different H2 rovibrational states are calculated up to 3000 K. Special emphasis is made on ortho/para conversion processes in which the parity j of the H2(j) states changes.

Extended analysis of the high resolution FTIR spectrum of 32S16O2 in the region of the ν2 band: Line positions, strengths, and pressure broadening widths

NASA Astrophysics Data System (ADS)

Ulenikov, O. N.; Bekhtereva, E. S.; Gromova, O. V.; Quack, M.; Mellau, G. Ch.; Sydow, C.; Bauerecker, S.

2018-05-01

The high resolution infrared spectra of sulfur dioxide (32S16O2) were recorded with a Bruker IFS 125HR Fourier transform infrared spectrometer (Zürich prototype ZP2001) in combination with a Ge:Cu detector and analyzed in the ν2 fundamental band region (400-650 cm-1 , ν0 ˜ = 517.8725691(77) cm-1). More than 4200 transitions were assigned in the experimental spectra to the ν2 band (the maximum values of the quantum numbers are Jmax. = 96 and Kamax. = 25). The subsequent weighted fit of experimentally assigned transitions was made with the Watson Hamiltonian. The 148 highly accurate MW transitions known from the literature have been also taken into account in the fit, resulting in a set of 33 parameters which reproduces the initial 1295 infrared ro-vibrational energy values from more than 4200 experimental line positions with a root mean square deviation drms = 1.5 ×10-4 cm-1. An analysis of 992 experimental ro-vibrational line intensities of the ν2 band was made, and a set of four effective dipole moment parameters was obtained which reproduces the initial experimental line intensities with a relative drms = 5.7 % . The half-widths of 146 ro-vibrational lines (Jmax. = 53 and Kamax. = 20) were analyzed from the multi-spectrum fit, and self-pressure broadening coefficients were determined.

A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Hua-Gen; Song, Hongwei; Yang, Minghui

Here, we report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C 2H 3. The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C 2H 3. All well converged 158 vibrational bands up to 3200 cm -1 are determined, together with a comparison to previous calculations and experimental results. Our results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from thatmore » of previous reduced dimensional calculations. The rotational constants of the fundamental vibrational bands of C 2H 3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. Additionally, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C 2H 3 without the requirement of explicit wavefunctions.« less

A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C2H3.

PubMed

Yu, Hua-Gen; Song, Hongwei; Yang, Minghui

2017-06-14

We report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C 2 H 3 . The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C 2 H 3 . All well converged 158 vibrational bands up to 3200 cm -1 are determined, together with a comparison to previous calculations and experimental results. Results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from that of previous reduced dimensional calculations. The rotational constants of the fundamental vibrational bands of C 2 H 3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. In addition, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C 2 H 3 without the requirement of explicit wavefunctions.

A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3

DOE PAGES

Yu, Hua-Gen; Song, Hongwei; Yang, Minghui

2017-06-12

Here, we report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C 2H 3. The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C 2H 3. All well converged 158 vibrational bands up to 3200 cm -1 are determined, together with a comparison to previous calculations and experimental results. Our results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from thatmore » of previous reduced dimensional calculations. The rotational constants of the fundamental vibrational bands of C 2H 3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. Additionally, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C 2H 3 without the requirement of explicit wavefunctions.« less

High Precision Rovibrational Spectroscopy of OH+

NASA Astrophysics Data System (ADS)

Markus, Charles R.; Hodges, James N.; Perry, Adam J.; Kocheril, G. Stephen; Müller, Holger S. P.; McCall, Benjamin J.

2016-02-01

The molecular ion OH+ has long been known to be an important component of the interstellar medium. Its relative abundance can be used to indirectly measure cosmic ray ionization rates of hydrogen, and it is the first intermediate in the interstellar formation of water. To date, only a limited number of pure rotational transitions have been observed in the laboratory making it necessary to indirectly calculate rotational levels from high-precision rovibrational spectroscopy. We have remeasured 30 transitions in the fundamental band with MHz-level precision, in order to enable the prediction of a THz spectrum of OH+. The ions were produced in a water cooled discharge of O2, H2, and He, and the rovibrational transitions were measured with the technique Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy. These values have been included in a global fit of field free data to a 3Σ- linear molecule effective Hamiltonian to determine improved spectroscopic parameters which were used to predict the pure rotational transition frequencies.

Measurement and computations of line shape parameters for the 12201 ← 03301, 11101 ← 10002 and 12201 ← 11102 self-broadened CO2 Q-branches

NASA Astrophysics Data System (ADS)

Al Mashwood, Abdullah; Predoi-Cross, Adriana; Devi, V. Malathy; Rozario, Hoimonti; Billinghurst, Brant

2018-06-01

Pure CO2 spectra recorded at room temperature and different pressures (0.2-140 Torr) have been analyzed with the help of a fitting routine that takes into account asymmetries arising in the spectral lines due to pressure induced effects such as line mixing. The fitting procedure used in this study allows one to adjust the ro-vibrational constants for the band rather than fitting for individual line parameters. These constrained parameters greatly reduce the measurement uncertainties and allow us to observe the behavior of the weak lines corresponding to high J quantum numbers. We have also calculated line mixing parameters using approximations based on exponential nature of the energy difference between ground and upper vibrational states involved in the ro-vibrational band transitions. The calculated results show good agreement when compared with the experimentally determined parameters.

Multiplexed direct-frequency-comb Vernier spectroscopy of carbon dioxide 2ν1 + ν3 ro-vibrational combination band

NASA Astrophysics Data System (ADS)

Siciliani de Cumis, M.; Eramo, R.; Coluccelli, N.; Galzerano, G.; Laporta, P.; Cancio Pastor, P.

2018-03-01

We investigated a set of nineteen 12C16O2 transitions of the 2ν1 + ν3 ro-vibrational band in the spectral region from 5064 to 5126 cm-1 at different pressures, using frequency-comb Vernier spectroscopy. Our spectrometer enabled the systematic acquisition of molecular absorption profiles with high precision. Spectroscopic parameters, namely, transition frequency, linestrength, and self-pressure broadening coefficient, have been accurately determined by using a global fit procedure. These data are in agreement with theoretical values contained in HITRAN2016 database [I. E. Gordon et al., J. Quant. Spectrosc. Radiat. Transfer 203, 3-69 (2017)] at the same precision level. A moderate improvement of the line intensity determinations, by a factor 1.5 in the best case [P(10) transition at 5091.6 cm-1], should be noticed, projecting direct-comb-Vernier-spectroscopy as an adequate tool for spectral intensity calibration.

Ro-vibrational spectrum of H2O-Ne in the ν2 H2O bending region: A combined ab initio and experimental investigation

NASA Astrophysics Data System (ADS)

Liu, Xunchen; Hou, Dan; Thomas, Javix; Li, Hui; Xu, Yunjie

2016-12-01

High resolution ro-vibrational transitions of the H2O-Ne complex in the ν2 bending region of H2O at 6 μm have been measured using a rapid scan infrared spectrometer based on an external cavity quantum cascade laser and an astigmatic multipass optical cell. To aid the spectral assignment, a four-dimension potential energy surface of H2O-Ne which depends on the intramolecular bending coordinate of the H2O monomer and the three intermolecular vibrational coordinates has been constructed and the rovibrational transitions have been calculated. Three ortho and two para H2O-20Ne bands have been identified from the experimental spectra. Some weaker transitions belonging to H2O-22Ne have also been identified experimentally. Spectroscopic fits have been performed for both the experimental and theoretical transition frequencies using a simple pseudo-diatomic Hamiltonian including both Coriolis coupling and Fermi resonance terms. The experimental and theoretical spectroscopic constants thus obtained have been compared. Further improvements needed in the potential energy surface and the related spectral simulation have been discussed.

Photodissociation of CS from Excited Rovibrational Levels

NASA Astrophysics Data System (ADS)

Pattillo, R. J.; Cieszewski, R.; Stancil, P. C.; Forrey, R. C.; Babb, J. F.; McCann, J. F.; McLaughlin, B. M.

2018-05-01

Accurate photodissociation cross sections have been computed for transitions from the X 1Σ+ ground electronic state of CS to six low-lying excited electronic states. New ab initio potential curves and transition dipole moment functions have been obtained for these computations using the multi-reference configuration interaction approach with the Davidson correction (MRCI+Q) and aug-cc-pV6Z basis sets. State-resolved cross sections have been computed for transitions from nearly the full range of rovibrational levels of the X 1Σ+ state and for photon wavelengths ranging from 500 Å to threshold. Destruction of CS via predissociation in highly excited electronic states originating from the rovibrational ground state is found to be unimportant. Photodissociation cross sections are presented for temperatures in the range between 1000 and 10,000 K, where a Boltzmann distribution of initial rovibrational levels is assumed. Applications of the current computations to various astrophysical environments are briefly discussed focusing on photodissociation rates due to the standard interstellar and blackbody radiation fields.

Rovibrational line-shape parameters for H2 in He and new H2-He potential energy surface

NASA Astrophysics Data System (ADS)

Thibault, Franck; Patkowski, Konrad; Żuchowski, Piotr S.; Jóźwiak, Hubert; Ciuryło, Roman; Wcisło, Piotr

2017-11-01

We report a new H2-He potential energy surface that, with respect to the previous one [Bakr et al.(2013)], covers much larger range of H2 stretching and exhibits more accurate asymptotic behavior for large separations between H2 and He. Close-coupling calculations performed on this improved potential energy surface allow us to provide line shape parameters for H2 between 5 and 2000 K for Raman isotropic Q lines and anisotropic Q lines (or electric quadrupole lines) and for vibrational bands from the ground up to v = 5 and rotational quantum numbers up to j = 5 . The parameters provided include the usual pressure -broadening and -shifting coefficients as well as the real and imaginary part of Dicke contribution to the Hess profile. The latter parameters can be readily implemented in other line-shape profiles like the most recent one of Hartmann and Tran.

Ghost features in Doppler-broadened spectra of rovibrational transitions in trapped HD+ ions

NASA Astrophysics Data System (ADS)

Patra, Sayan; Koelemeij, J. C. J.

2017-02-01

Doppler broadening plays an important role in laser rovibrational spectroscopy of trapped deuterated molecular hydrogen ions (HD+), even at the millikelvin temperatures achieved through sympathetic cooling by laser-cooled beryllium ions. Recently, Biesheuvel et al. (2016) presented a theoretical lineshape model for such transitions which not only considers linestrengths and Doppler broadening, but also the finite sample size and population redistribution by blackbody radiation, which are important in view of the long storage and probe times achievable in ion traps. Here, we employ the rate equation model developed by Biesheuvel et al. to theoretically study the Doppler-broadened hyperfine structure of the (v, L) : (0, 3) → (4, 2) rovibrational transition in HD+ at 1442 nm. We observe prominent yet hitherto unrecognized ghost features in the simulated spectrum, whose positions depend on the Doppler width, transition rates, and saturation levels of the hyperfine components addressed by the laser. We explain the origin and behavior of such features, and we provide a simple quantitative guideline to assess whether ghost features may appear. As such ghost features may be common to saturated Doppler-broadened spectra of rotational and vibrational transitions in trapped ions composed of partly overlapping lines, our work illustrates the necessity to use lineshape models that take into account all the relevant physics.

HO2 rovibrational eigenvalue studies for nonzero angular momentum

NASA Astrophysics Data System (ADS)

Wu, Xudong T.; Hayes, Edward F.

1997-08-01

An efficient parallel algorithm is reported for determining all bound rovibrational energy levels for the HO2 molecule for nonzero angular momentum values, J=1, 2, and 3. Performance tests on the CRAY T3D indicate that the algorithm scales almost linearly when up to 128 processors are used. Sustained performance levels of up to 3.8 Gflops have been achieved using 128 processors for J=3. The algorithm uses a direct product discrete variable representation (DVR) basis and the implicitly restarted Lanczos method (IRLM) of Sorensen to compute the eigenvalues of the polyatomic Hamiltonian. Since the IRLM is an iterative method, it does not require storage of the full Hamiltonian matrix—it only requires the multiplication of the Hamiltonian matrix by a vector. When the IRLM is combined with a formulation such as DVR, which produces a very sparse matrix, both memory and computation times can be reduced dramatically. This algorithm has the potential to achieve even higher performance levels for larger values of the total angular momentum.

Heterodyne frequency measurements on N2O at 5.3 and 9.0 microns

NASA Technical Reports Server (NTRS)

Wells, J. S.; Jennings, D. A.; Hinz, A.; Murray, J. S.; Maki, A. G.

1985-01-01

Heterodyne frequency measurements on the 01(1)1-00(0)0 band of N2O have been made with the use of a tunable-diode laser, CO laser transfer oscillator, and a CO2 laser frequency synthesizer. A beat frequency was measured between a CO laser and tunable-diode laser whose frequency was locked to the peak of N2O absorption features. The frequency of the CO laser was simultaneously determined by neasuring the beat frequency with respect to a reference synthesized from two CO2 lasers. New rovibrational constants are given for the 01(1)1 state of N2O, which are in excellent agreement with previous results, although the band center is 4 MHz higher than in the previous measurements. A table for the line frequencies and their absolute uncertainties is given for the N2O absorption lines in the wave-number region from 1830 to 1920 kaysers. Some additional frequency measurements near the lower-frequency end of the 02(0)0-00(0)0 band have also been made with respect to a C-12)(0-18)2 laser.

High Spectral Resolution SOFIA/EXES Observations of C2H2 toward Orion IRc2

NASA Astrophysics Data System (ADS)

Rangwala, Naseem; Colgan, Sean W. J.; Le Gal, Romane; Acharyya, Kinsuk; Huang, Xinchuan; Lee, Timothy J.; Herbst, Eric; deWitt, Curtis; Richter, Matt; Boogert, Adwin; McKelvey, Mark

2018-03-01

We present high spectral resolution observations from 12.96 to 13.33 microns toward Orion IRc2 using the mid-infrared spectrograph, Echelon-Cross-Echelle Spectrograph (EXES), at Stratospheric Observatory for Infrared Astronomy (SOFIA). These observations probe the physical and chemical conditions of the Orion hot core, which is sampled by a bright, compact, mid-infrared background continuum source in the region, IRc2. All 10 of the rovibrational C2H2 transitions expected in our spectral coverage are detected with high signal-to-noise ratios (S/Ns), yielding continuous coverage of the R-branch lines from J = 9–8 to J = 18–17, including both ortho and para species. Eight of these rovibrational transitions are newly reported detections. The isotopologue, 13CCH2, is clearly detected with a high S/N. This enabled a direct measurement of the 12C/13C isotopic ratio for the Orion hot core of 14 ± 1 and an estimated maximum value of 21. We also detected several HCN rovibrational lines. The ortho and para C2H2 ladders are clearly separate, and tracing two different temperatures, 226 K and 164 K, respectively, with a non-equilibrium ortho to para ratio (OPR) of 1.7 ± 0.1. Additionally, the ortho and para V LSR values differ by about 1.8 ± 0.2 km s‑1, while the mean line widths differ by 0.7 ± 0.2 km s‑1, suggesting that these species are not uniformly mixed along the line of sight to IRc2. We propose that the abnormally low C2H2 OPR could be a remnant from an earlier, colder phase, before the density enhancement (now the hot core) was impacted by shocks generated from an explosive event 500 years ago.

Titan's Ionic Species: Theoretical Treatment of N2H+ and Related Ions

NASA Astrophysics Data System (ADS)

Brites, V.; Hochlaf, M.

2009-06-01

We use different ab initio methods to compute the three-dimensional potential energy surface (3D-PES) of the ground state of N2H+. This includes the standard coupled cluster, the complete active space self-consistent field, the internally contacted multi reference configuration interaction, and the newly developed CCSD(T)-F12 methods. For the description of H and N atoms, several basis sets are tested. Then, we incorporate the 3D-PES analytical representations into variational calculations of the rovibrational spectrum of N2H+(X˜1Σ+) up to 7200 cm-1 above the zero point vibrational energy. Our data show that the CCSD(T)-F12/aug-cc-pVTZ approach represents a compromise for good description of the PES and computation cost. This technique is recommended for full dimensional PES generation of atmospheric and astrophysical relevant polyatomic systems. We applied this method to derive the rovibrational spectra of N2H+(X˜1Σ+) and of N2H++(X˜2Σ+). Finally, we discuss the existence of the N2H++(X˜2Σ+) in Titan's atmosphere.

Numerically Exact Calculation of Rovibrational Levels of Cl^-H_2O

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2014-06-01

Large amplitude vibrations of Van der Waals clusters are important because they reveal large regions of a potential energy surface (PES). To calculate spectra of Van der Waals clusters it is common to use an adiabatic approximation. When coupling between intra- and inter-molecular coordinates is important non-adiabatic coupling cannot be neglected and it is therefore critical to develop and test theoretical methods that couple both types of coordinates. We have developed new product basis and contracted basis Lanczos methods for Van der Waals complexes and tested them by computing rovibrational energy levels of Cl^-H_2O. The new product basis is made of functions of the inter-monomer distance, Wigner functions that depend on Euler angles specifying the orientation of H_2O with respect to a frame attached to the inter-monomer Jacobi vector, basis functions for H_2O vibration, and Wigner functions that depend on Euler angles specifying the orientation of the inter-monomer Jacobi vector with respect to a space-fixed frame. An advantage of this product basis is that it can be used to make an efficient contracted basis by replacing the vibrational basis functions for the monomer with monomer vibrational wavefunctions. Due to weak coupling between intra- and inter-molecular coordinates, only a few tens of monomer vibrational wavefunctions are necessary. The validity of the two new methods is established by comparing energy levels with benchmark rovibrational levels obtained with polyspherical coordinates and spherical harmonic type basis functions. For all bases, product structure is exploited to calculate eigenvalues with the Lanczos algorithm. For Cl^-H_2O, we are able, for the first time, to compute accurate splittings due to tunnelling between the two equivalent C_s minima. We use the PES of Rheinecker and Bowman (RB). Our results are in good agreement with experiment for the five fundamental bands observed. J. Rheinecker and J. M. Bowman, J. Chem. Phys. 124 131102

Rovibrational hybrid fs/ps CARS using a volume Bragg grating for N₂ thermometry.

PubMed

Scherman, M; Nafa, M; Schmid, T; Godard, A; Bresson, A; Attal-Tretout, B; Joubert, P

2016-02-01

Coherent anti-Stokes Raman scattering (CARS) spectra of N2 in the hybrid femtosecond/picosecond regime have been recorded with 0.7  cm(-1) resolution. The Q-branch rovibrational structure has been resolved, making it suitable for gas-phase simultaneous rotational and vibrational thermometry applications. Resolving this spectral structure requires synchronization of a narrowband picosecond probe pulse with a broadband femtosecond pair of pump and Stokes pulses. It is achieved using a single femtosecond ytterbium-laser source and a volume Bragg grating in a compact experimental arrangement.

Line intensities of the 30011e - 00001e band of 12C16O2by laser-locked cavity ring-down spectroscopy

NASA Astrophysics Data System (ADS)

Kang, P.; Wang, J.; Liu, G.-L.; Sun, Y. R.; Zhou, Z.-Y.; Liu, A.-W.; Hu, S.-M.

2018-03-01

Thirty well isolated ro-vibrational transitions of the 30011e - 00001e band of 12C16O2 at 1.54 μm have been recorded with a laser-locked cavity ring-down spectrometer. The line intensities were obtained with accuracies better than 0.85%. Comparisons of the line intensities determined in this work with literature experimental values and those from HITRAN2016, AMES, UCL-IAO and CDSD-296 line lists are given.

Microwave Fourier transform spectroscopy of rotational and rovibrational transitions in the {ν 2}/{ν 4} dyad of silane- 28Si

NASA Astrophysics Data System (ADS)

Oldani, M.; Bauder, A.; Pierre, G.

1986-06-01

Rotational and rovibrational transitions of silane- 28Si in the {ν 2}/{ν 4} dyad have been observed directly with a pulsed microwave Fourier transform spectrometer operating in the 8- to 18-GHz frequency range. Seventeen transitions of the types ν4 ← ν4, ν2 ← ν2, ν2 ← ν4, and ν4 ← ν2 have been observed and assigned. The transitions are generally weaker than those of the vibrational ground state and weaker than the corresponding transitions of methane- d4. The observed microwave transitions have been analyzed in combination with previous high-resolution infrared measurements (G. Pierre, A. Valentin, and L. Henry, Canad. J. Phys. (1986), in press) in a least-squares fit of the vibration-rotation constants t s,s'Ω(K,n Γ) of the {ν 2}/{ν 4}- dyad Hamiltonian.

Precision Measurement of the Rovibrational Energy-Level Structure of ^{4}He^{+}_{2}

NASA Astrophysics Data System (ADS)

Semeria, Luca; Jansen, Paul; Agner, Josef A.; Schmutz, Hansjürg; Merkt, Frederic

2017-06-01

He_{2}^{+} is a three-electron system for which highly accurate ab initio calculations are possible. The latest calculations of the rovibrational energies of He_{2}^{+} by Tung et al. have a reported accuracy of 120 MHz, although they do not include relativistic and quantum electrodynamics (QED) effects. We determined the rovibrational structure of ^{4}He^{+}_{2} from measurements of the Rydberg spectrum of metastable a ^3Σ_u^+ He_{2} (He^{*}_{2} hereafter) and Rydberg-series extrapolation using multichannel quantum-defect-theory. He^{*}_{2} molecules are produced in supersonic beams with velocities tunable down to about 100 m/s by combining a cryogenic supersonic-beam source with a multistage Zeeman decelerator. They are then excited to high-np Rydberg states by single-photon excitation. In the experiments, we use a pulsed uv laser system, with a near Fourier-transform-limited bandwidth of 150 MHz. The Zeeman deceleration reduces the systematic uncertainty arising from a possible Doppler shift and greatly simplifies the spectral assignment because of its spin-rotational state selectivity. Results will be presented on the rotational structure of the lowest three vibrational levels of He^{+}_{2}. The unprecedented accuracy that we have obtained for the v^{+}=0 rotational intervals of He_{2}^{+} enables the quantification of the relativistic and QED corrections by comparison with the results of Tung et al.^a W.-C. Tung, M. Pavanello and L. Adamowicz, J. Chem. Phys., 136, 104309, 2012. C. Jungen, Elements of Quantum Defect Theory, in : Handbook of High-resolution Spectroscopy, 2001. D. Sprecher, J. Liu, T. Krähenmann, M. Schäfer, and F. Merkt, J. Chem. Phys., 140, 064304, 2014. A. W. Wiederkehr, S. D. Hogan, M. Andrist, H. Schmutz, B. Lambillotte, J. A. Agner, and F. Merkt., J. Chem. Phys., 135, 214202, 2011. M. Motsch, P. Jansen, J. A. Agner, H. Schmutz, and F. Merkt, Phys. Rev. A, 89, 043420, 2014. P. Jansen, L. Semeria, L. E. Hofer, S. Scheidegger, J. A. Agner

Rovibrational intensities and electric dipole moment function of the X2 Pi hydroxyl radical

NASA Technical Reports Server (NTRS)

Chackerian, C., Jr.; Goorvitch, D.; Benidar, A.; Farrenq, R.; Guelachvili, G.; Martin, P. M.; Abrams, M. C.; Davis, S. P.

1992-01-01

Recent work aimed at determining the absolute rovibrational transition intensities for the ground electronic state of the hydroxyl radical is reviewed. Two new sets of Fourier transform emission spectra of OH are described which were recorded at the University of Paris and at the Kitt Peak National Solar Observatory.

Rovibrational Quantum Dynamics of the Methane-Water Dimer

NASA Astrophysics Data System (ADS)

Sarka, János; Császár, Attila; Mátyus, Edit

2017-06-01

The challenging quantum dynamical description of the CH_4.H_2O complex has been solved variationally to provide theoretical explanation and assignment to the high-resolution spectroscopic measurements of the methane-water dimer carried out some twenty years ago. The computational results are in excellent agreement with the reported experimental transitions and the experimentally observed reversed rovibrational sequences, i.e., formally negative rotational excitation energies, are also obtained in the computations. In order to better understand the origin of these peculiar features in the energy-level spectrum, we studied all four possible combinations of the light and heavy isotopologues of methane and water and analyzed their rovibrational states using two limiting model systems: the rigidly rotating (RR) molecule and the coupled rotor (CR) system corresponding to the coupling of the two rotating monomers. All rovibrational quantum dynamical computations^{a,c} were carried out with rigid monomers and J = 0,1,2 total angular momentum quantum numbers using the fourth-age quantum chemical code GENIUSH and two different methane-water potential energy surfaces (PES). The numerical and formal analysis of the wave functions give insight into a fascinating complex world worth for further theoretical and experimental inquiries. J. Sarka, A. G. Császár, S. C. Althorpe, D. J. Wales and E. Mátyus, Phys. Chem. Chem. Phys. 18, 22816 (2016). L. Dore, R. C. Cohen, C. A. Schmuttenmaer, K. L. Busarow, M. J. Elrod, J. G. Loeser and R. J. Saykally, J. Chem. Phys. 100, 863 (1994). J. Sarka, A. G. Császár and E. Mátyus, Phys. Chem. Chem. Phys. accepted for publication (2017).} E. Mátyus, G. Czakó and A. G. Császár, J. Chem. Phys. 130, 134112 (2009). C. Fábri, E. Mátyus and A. G. Császár, J. Chem. Phys. 134, 074105 (2011). O. Akin-Ojo and K. Szalewicz, J. Chem. Phys. 123, 134311 (2005). C. Qu, R. Conte, P. L. Houston and J. M. Bowman, Phys. Chem. Chem. Phys. 17, 8172 (2015).

Rapid-Adiabatic Control of Ro-Vibrational Populations in Polyatomic Molecules

NASA Astrophysics Data System (ADS)

Zak, Emil J.; Yachmenev, Andrey

2017-06-01

We present a simple method for control of ro-vibrational populations in polyatomic molecules in the presence of inhomogeneous electric fields [1]. Cooling and trapping of heavy polar polyatomic molecules has become one of the frontier goals in high-resolution molecular spectroscopy, especially in the context of parity violation measurement in chiral compounds [2]. A key step toward reaching this goal would be development of a robust and efficient protocol for control of populations of ro-vibrational states in polyatomic, often floppy molecules. Here we demonstrate a modification of the stark-chirped rapid-adiabatic-passage technique (SCRAP) [3], designed for achieving high levels of control of ro-vibrational populations over a selected region in space. The new method employs inhomogeneous electric fields to generate space- and time- controlled Stark-shifts of energy levels in molecules. Adiabatic passage between ro-vibrational states is enabled by the pump pulse, which raises the value of the Rabi frequency. This Stark-chirped population transfer can be used in manipulation of population differences between high-field-seeking and low-field-seeking states of molecules in the Stark decelerator [4]. Appropriate timing of voltages on electric rods located along the decelerator combined with a single pump laser renders our method as potentially more efficient than traditional Stark decelerator techniques. Simulations for NH_3 show significant improvement in effectiveness of cooling, with respect to the standard 'moving-potential' method [5]. At the same time a high phase-space acceptance of the molecular packet is maintained. E. J. Zak, A. Yachmenev (submitted). C. Medcraft, R. Wolf, M. Schnell, Angew. Chem. Int. Ed., 53, 43, 11656-11659 (2014) M. Oberst, H. Munch, T. Halfman, PRL 99, 173001 (2007). K. Wohlfart, F. Grätz, F. Filsinger, H. Haak, G. Meijer, J. Küpper, Phys. Rev. A 77, 031404(R) (2008). H. L. Bethlem, F. M. H. Crompvoets, R. T. Jongma, S. Y. T. van de

The role of axis embedding on rigid rotor decomposition analysis of variational rovibrational wave functions.

PubMed

Szidarovszky, Tamás; Fábri, Csaba; Császár, Attila G

2012-05-07

Approximate rotational characterization of variational rovibrational wave functions via the rigid rotor decomposition (RRD) protocol is developed for Hamiltonians based on arbitrary sets of internal coordinates and axis embeddings. An efficient and general procedure is given that allows employing the Eckart embedding with arbitrary polyatomic Hamiltonians through a fully numerical approach. RRD tables formed by projecting rotational-vibrational wave functions into products of rigid-rotor basis functions and previously determined vibrational eigenstates yield rigid-rotor labels for rovibrational eigenstates by selecting the largest overlap. Embedding-dependent RRD analyses are performed, up to high energies and rotational excitations, for the H(2) (16)O isotopologue of the water molecule. Irrespective of the embedding chosen, the RRD procedure proves effective in providing unambiguous rotational assignments at low energies and J values. Rotational labeling of rovibrational states of H(2) (16)O proves to be increasingly difficult beyond about 10,000 cm(-1), close to the barrier to linearity of the water molecule. For medium energies and excitations the Eckart embedding yields the largest RRD coefficients, thus providing the largest number of unambiguous rotational labels.

Anharmonic Rovibrational Partition Functions for Fluxional Species at High Temperatures via Monte Carlo Phase Space Integrals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jasper, Ahren W.; Gruey, Zackery B.; Harding, Lawrence B.

Monte Carlo phase space integration (MCPSI) is used to compute full dimensional and fully anharmonic, but classical, rovibrational partition functions for 22 small- and medium-sized molecules and radicals. Several of the species considered here feature multiple minima and low-frequency nonlocal motions, and efficiently sampling these systems is facilitated using curvilinear (stretch, bend, and torsion) coordinates. The curvilinear coordinate MCPSI method is demonstrated to be applicable to the treatment of fluxional species with complex rovibrational structures and as many as 21 fully coupled rovibrational degrees of freedom. Trends in the computed anharmonicity corrections are discussed. For many systems, rovibrational anharmonicities atmore » elevated temperatures are shown to vary consistently with the number of degrees of freedom and with temperature once rovibrational coupling and torsional anharmonicity are accounted for. Larger corrections are found for systems with complex vibrational structures, such as systems with multiple large-amplitude modes and/or multiple minima.« less

Determination of the vinyl fluoride line intensities by TDL spectroscopy: the object oriented approach of Visual Line Shape Fitting Program to line profile analysis

NASA Astrophysics Data System (ADS)

Tasinato, Nicola; Pietropolli Charmet, Andrea; Stoppa, Paolo; Giorgianni, Santi

2010-03-01

In this work the self-broadening coefficients and the integrated line intensities for a number of ro-vibrational transitions of vinyl fluoride have been determined for the first time by means of TDL spectroscopy. The spectra recorded in the atmospheric window around 8.7 µm appear very crowded with a density of about 90 lines per cm-1. In order to fit these spectral features a new fitting software has been implemented. The program, which is designed for laser spectroscopy, can fit many lines simultaneously on the basis of different theoretical profiles (Doppler, Lorentz, Voigt, Galatry and Nelkin-Ghatak). Details of the object oriented implementation of the application are given. The reliability of the program is demonstrated by determining the line parameters of some ro-vibrational lines of sulphur dioxide in the ν1 band region around 9 µm. Then the software is used for the line profile analysis of vinyl fluoride. The experimental line shapes show deviations from the Voigt profile, which can be well modelled by using a Dicke narrowed line shape function. This leads to the determination of the self-narrowing coefficient within the framework of the strong collision model.

Ames S-32 O-16 O-18 Line List for High-Resolution Experimental IR Analysis

NASA Technical Reports Server (NTRS)

Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

2016-01-01

By comparing to the most recent experimental data and spectra of the SO2 628 ?1/?3 bands (see Ulenikov et al., JQSRT 168 (2016) 29-39), this study illustrates the reliability and accuracy of the Ames-296K SO2 line list, which is accurate enough to facilitate such high-resolution spectroscopic analysis. The SO2 628 IR line list is computed on a recently improved potential energy surface (PES) refinement, denoted Ames-Pre2, and the published purely ab initio CCSD(T)/aug-cc-pVQZ dipole moment surface. Progress has been made in both energy level convergence and rovibrational quantum number assignments agreeing with laboratory analysis models. The accuracy of the computed 628 energy levels and line list is similar to what has been achieved and reported for SO2 626 and 646, i.e. 0.01-0.03 cm(exp -1) for bands up to 5500 cm(exp -1). During the comparison, we found some discrepancies in addition to overall good agreements. The three-IR-list based feature-by-feature analysis in a 0.25 cm(exp -1) spectral window clearly demonstrates the power of the current Ames line lists with new assignments, correction of some errors, and intensity contributions from varied sources including other isotopologues. We are inclined to attribute part of detected discrepancies to an incomplete experimental analysis and missing intensity in the model. With complete line position, intensity, and rovibrational quantum numbers determined at 296 K, spectroscopic analysis is significantly facilitated especially for a spectral range exhibiting such an unusually high density of lines. The computed 628 rovibrational levels and line list are accurate enough to provide alternatives for the missing bands or suspicious assignments, as well as helpful to identify these isotopologues in various celestial environments. The next step will be to revisit the SO2 828 and 646 spectral analyses.

RichMol: A general variational approach for rovibrational molecular dynamics in external electric fields

NASA Astrophysics Data System (ADS)

Owens, Alec; Yachmenev, Andrey

2018-03-01

In this paper, a general variational approach for computing the rovibrational dynamics of polyatomic molecules in the presence of external electric fields is presented. Highly accurate, full-dimensional variational calculations provide a basis of field-free rovibrational states for evaluating the rovibrational matrix elements of high-rank Cartesian tensor operators and for solving the time-dependent Schrödinger equation. The effect of the external electric field is treated as a multipole moment expansion truncated at the second hyperpolarizability interaction term. Our fully numerical and computationally efficient method has been implemented in a new program, RichMol, which can simulate the effects of multiple external fields of arbitrary strength, polarization, pulse shape, and duration. Illustrative calculations of two-color orientation and rotational excitation with an optical centrifuge of NH3 are discussed.

Ames-2016 line lists for 13 isotopologues of CO2: Updates, consistency, and remaining issues

NASA Astrophysics Data System (ADS)

Huang (黄新川), Xinchuan; Schwenke, David W.; Freedman, Richard S.; Lee, Timothy J.

2017-12-01

A new 626-based Ames-2 PES refinement and Ames-2016 line lists for 13 CO2 isotopologues are reported. A consistent σRMS = ±0.02 cm-1 is established for hundreds of isotopologue band origins using the Ames-2 PES. Ames-2016 line lists are computed at 296 K, 1000 K and 4000 K using the Ames-2 PES and the same DMS-N2 dipole surface used previously, with J up to 150, E‧ up to 24,000 cm-1 or 18,000 cm-1 and appropriate intensity cutoffs. The lists are compared to the CDSD-296, CDSD-4000 databases, UCL line lists, and a few recent highly accurate CO2 intensity measurements. Both agreements and discrepancies are discussed. Compared to the old Ames CO2 lists, the Ames-2016 line lists have line position deviations reduced by 50% or more, which consequently leads to more reliable intensities. The line shape parameters in the Ames-2016 line lists are predicted using the newly assigned conventional vibrational polyad quantum numbers for rovibrational levels below 12,000 cm-1 so the quality of the line shape parameters is similar to that of CDSD or HITRAN. This study further proves that a semi-empirically refined PES (Ames-1 and Ames-2) coupled with a high quality ab initio DMS (DMS-N2 and UCL) may generate IR predictions with consistent accuracy and is thus helpful in the analysis of laboratory spectra and simulations of various isotopologues. The Ames-2016 lists based on DMS-N2 have reached the ∼1% intensity prediction accuracy level for the recent 626 30013-00001 and 20013-00001 bands, but further quantification and improvements require sub-percent or sub-half-percent accurate experimental intensities. The inter-isotopologue consistency of the intensity prediction accuracies should have reached better than 1-3% for regular bands not affected by resonances. Since the Effective Dipole Models (EDM) in CDSD and HITRAN have 1-20% or even larger uncertainties, we show that the Ames lists can provide better alternative IR data for many hard-to-determine isotopologue bands

On the Lowest Ro-Vibrational States of Protonated Methane: Experiment and Analytical Model

NASA Astrophysics Data System (ADS)

Schmiedt, Hanno; Jensen, Per; Asvany, Oskar; Schlemmer, Stephan

2016-06-01

Protonated methane, CH_5^+, is the prototype of an extremely floppy molecule. To the best of our knowledge all barriers are surmountable in the rovibrational ground state; the large amount of zero-point vibrational energy leads to large amplitude motions for many degrees of freedom. Low resolution but broad band vibrational spectroscopy [1] revealed an extremely wide range of C-H stretching vibrations. Comparison with theoretical IR spectra supported the structural motif of a CH_3 tripod and an H_2 moiety, bound to the central carbon atom by a 3c2e bond. In a more dynamic picture the five protons surround the central carbon atom without significant restrictions on the H-C-H bending or H_n-C torsional motions. The large-amplitude internal motions preclude a simple theoretical description of the type possible for more conventional molecules, such as the related spherical-top methane molecule. Recent high-resolution ro-vibrational spectra obtained in cold ion trap experiments [2] show that the observed CH_5^+ transitions belong to a very well-defined energy level scheme describing the lowest rotational and vibrational states of this enigmatic molecule. Here we analyse the experimental ground state combination differences and associate them with the motional states of CH_5^+ allowed by Fermi-Dirac statistics. A model Hamiltonian for unrestricted internal rotations in CH_5^+ yields a simple analytical expression for the energy eigenvalues, expressed in terms of new quantum numbers describing the free internal rotation. These results are compared to the experimental combination differences and the validity of the model will be discussed together with the underlying assumptions. [1] O. Asvany, P. Kumar, I. Hegemann, B. Redlich, S. Schlemmer and D. Marx, Science 309, (2005) 1219-1222 [2] O. Asvany, K.M.T. Yamada, S. Brünken, A. Potapov, S. Schlemmer, Science 347 (2015) 1346-1349

A comment on "Ab initio study: the potential energy curves and ro-vibrational spectrum of low-lying excited states of HCl+ cation"

NASA Astrophysics Data System (ADS)

Liu, Ya-Jun; Cheng, Xin-Lu; Chen, Hua-Jun; Cheng, Jun-Xia; Song, Xiao-Shu

2018-02-01

Since the 2Π state in HCl+ is an inverted doublet, the energy of the 2Π1/2 state is higher than the 2Π3/2. Therefore, the larger value of intensity correspond to the transition of 2Π3/2. We calculated the Einstein A coefficients and radiation lifetimes for the A2Σ+-X2Π transition. Our results are in good agreement with the experimental data and theoretical values. Then the ro-vibrational line intensities of the 1-0 band were calculated for the 2Π3/2 and 2Π1/2 states of HCl+. Employing the RKR potential, the predicted band origins for Δν=1-0 are 2569.3 and 2568.55 cm-1 for 2Π3/2 and 2Π1/2, respectively.

Understanding nuclear motions in molecules: Derivation of Eckart frame ro-vibrational Hamiltonian operators via a gateway Hamiltonian operator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szalay, Viktor, E-mail: szalay.viktor@wigner.mta.hu

A new ro-vibrational Hamiltonian operator, named gateway Hamiltonian operator, with exact kinetic energy term, T-hat, is presented. It is in the Eckart frame and it is of the same form as Watson’s normal coordinate Hamiltonian. However, the vibrational coordinates employed are not normal coordinates. The new Hamiltonian is shown to provide easy access to Eckart frame ro-vibrational Hamiltonians with exact T-hat given in terms of any desired set of vibrational coordinates. A general expression of the Eckart frame ro-vibrational Hamiltonian operator is given and some of its properties are discussed.

Symmetry analysis of trimers rovibrational spectra: the case of Ne3★

NASA Astrophysics Data System (ADS)

Márquez-Mijares, Maykel; Roncero, Octavio; Villarreal, Pablo; González-Lezana, Tomás

2018-05-01

An approximate method to assign the symmetry to the rovibrational spectrum of homonuclear trimers based on the solution of the rotational Hamiltonian by means of a purely vibrational basis combined with standard rotational functions is applied on Ne3. The neon trimer constitutes an ideal test between heavier systems such as Ar3 for which the method proves to be an extremely useful technique and some other previously investigated cases such as H3 + where some limitations were observed. Comparisons of the calculated rovibrational energy levels are established with results from different calculations reported in the literature.

Laboratory measurements of VUV N2 photoabsorption cross sections and line widths: applications to planetary atmospheric transmission models

NASA Astrophysics Data System (ADS)

Smith, P. L.; Stark, G.; Yoshino, K.

2003-05-01

The analyses of VUV occultation measurements of the N2-rich atmospheres of Titan and Triton are hampered by the lack of fundamental spectroscopic data for N2. There is a need for reliable photoabsorption cross sections and line widths for the 100 electronic bands of N2 in the 80 to 100 nm wavelength region. We present analyses of new measurements of individual line strengths and widths in N2 bands in the region 94 to 100 nm. Within individual bands, we find significant departures from the predicted line strength distributions based on isolated band models. Line width analyses within each band indicate that predissociation-broadening is often highly dependent on the rotational quantum number. We illustrate the importance of N2 line widths in the analysis of occultation measurements via N2 transmission models over selected wavelength regions. We have continued to compile on-line molecular spectroscopic atlas based on our N2 laboratory data: http://cfa-www.harvard.edu/amdata/ampdata/N2ARCHIVE/n2home.html. The archive includes published and unpublished 14N2, 14N15N, and 15N2 line lists and spectroscopic identifications, excited state energy levels, band and line f-values, a summary of published band f-value and line width measurements, and a cross-referenced summary of the relevant N2 literature. The listings are searchable by wavelength interval or band identification and are suitable for down-loading in a convenient format. We gratefully acknowledge funding support from NASA grant NAG5-9059 and the Smithsonian Institution Atherton-Seidell Grant Program.

Quantum scattering calculations for ro-vibrational de-excitation of CO by hydrogen atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Lei; Avoird, Ad van der; Karman, Tijs

2015-05-28

We present quantum-mechanical scattering calculations for ro-vibrational relaxation of carbon monoxide (CO) in collision with hydrogen atoms. Collisional cross sections of CO ro-vibrational transitions from v = 1, j = 0 − 30 to v′ = 0, j′ are calculated using the close coupling method for collision energies between 0.1 and 15 000 cm{sup −1} based on the three-dimensional potential energy surface of Song et al. [J. Phys. Chem. A 117, 7571 (2013)]. Cross sections of transitions from v = 1, j ≥ 3 to v′ = 0, j′ are reported for the first time at this level of theory. Alsomore » calculations by the more approximate coupled states and infinite order sudden (IOS) methods are performed in order to test the applicability of these methods to H–CO ro-vibrational inelastic scattering. Vibrational de-excitation rate coefficients of CO (v = 1) are presented for the temperature range from 100 K to 3000 K and are compared with the available experimental and theoretical data. All of these results and additional rate coefficients reported in a forthcoming paper are important for including the effects of H–CO collisions in astrophysical models.« less

Nonlinear rovibrational polarization response of water vapor to ultrashort long-wave infrared pulses

NASA Astrophysics Data System (ADS)

Schuh, K.; Rosenow, P.; Kolesik, M.; Wright, E. M.; Koch, S. W.; Moloney, J. V.

2017-10-01

We study the rovibrational polarization response of water vapor using a fully correlated optical Bloch equation approach employing data from the HITRAN database. For a 10 -μ m long-wave infrared pulse the resulting linear response is negative, with a negative nonlinear response at intermediate intensities and a positive value at higher intensities. For a model atmosphere comprised of the electronic response of argon combined with the rovibrational response of water vapor this leads to a weakened positive nonlinear response at intermediate intensities. Propagation simulations using a simplified noncorrelated approach show the resultant reduction in the peak filament intensity sustained during filamentation due to the presence of the water vapor.

Simultaneous manipulation and observation of multiple ro-vibrational eigenstates in solid para-hydrogen.

PubMed

Katsuki, Hiroyuki; Ohmori, Kenji

2016-09-28

We have experimentally performed the coherent control of delocalized ro-vibrational wave packets (RVWs) of solid para-hydrogen (p-H 2 ) by the wave packet interferometry (WPI) combined with coherent anti-Stokes Raman scattering (CARS). RVWs of solid p-H 2 are delocalized in the crystal, and the wave function with wave vector k ∼ 0 is selectively excited via the stimulated Raman process. We have excited the RVW twice by a pair of femtosecond laser pulses with delay controlled by a stabilized Michelson interferometer. Using a broad-band laser pulse, multiple ro-vibrational states can be excited simultaneously. We have observed the time-dependent Ramsey fringe spectra as a function of the inter-pulse delay by a spectrally resolved CARS technique using a narrow-band probe pulse, resolving the different intermediate states. Due to the different fringe oscillation periods among those intermediate states, we can manipulate their amplitude ratio by tuning the inter-pulse delay on the sub-femtosecond time scale. The state-selective manipulation and detection of the CARS signal combined with the WPI is a general and efficient protocol for the control of the interference of multiple quantum states in various quantum systems.

Modelling non-adiabatic effects in H_3^+: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces

NASA Astrophysics Data System (ADS)

Mátyus, Edit; Szidarovszky, Tamás; Császár, Attila G.

2014-10-01

Introducing different rotational and vibrational masses in the nuclear-motion Hamiltonian is a simple phenomenological way to model rovibrational non-adiabaticity. It is shown on the example of the molecular ion H_3^+, for which a global adiabatic potential energy surface accurate to better than 0.1 cm-1 exists [M. Pavanello, L. Adamowicz, A. Alijah, N. F. Zobov, I. I. Mizus, O. L. Polyansky, J. Tennyson, T. Szidarovszky, A. G. Császár, M. Berg et al., Phys. Rev. Lett. 108, 023002 (2012)], that the motion-dependent mass concept yields much more accurate rovibrational energy levels but, unusually, the results are dependent upon the choice of the embedding of the molecule-fixed frame. Correct degeneracies and an improved agreement with experimental data are obtained if an Eckart embedding corresponding to a reference structure of D3h point-group symmetry is employed. The vibrational mass of the proton in H_3^+ is optimized by minimizing the root-mean-square (rms) deviation between the computed and recent high-accuracy experimental transitions. The best vibrational mass obtained is larger than the nuclear mass of the proton by approximately one third of an electron mass, m^(v)_opt,p=m_nuc,p+0.31224 m_e. This optimized vibrational mass, along with a nuclear rotational mass, reduces the rms deviation of the experimental and computed rovibrational transitions by an order of magnitude. Finally, it is shown that an extension of the algorithm allowing the use of motion-dependent masses can deal with coordinate-dependent mass surfaces in the rovibrational Hamiltonian, as well.

Experimental Study of Temperature-Dependence Laws of Non-Voigt Absorption Line Shape Parameters

NASA Astrophysics Data System (ADS)

Wilzewski, Jonas; Birk, Manfred; Loos, Joep; Wagner, Georg

2017-06-01

To improve the understanding of temperature-dependence laws of spectral line shape parameters, spectra of the ν_3 rovibrational band of CO_2 perturbed by 10, 30, 100, 300 and 1000 mbar of N_2 were measured at nine temperatures between 190 K and 330 K using a 22 cm long single-pass absorption cell in a Bruker IFS125 HR Fourier Transform spectrometer. The spectra were fitted employing a quadratic speed-dependent hard collision model in the Hartmann-Tran implementation extended to account for line mixing in the Rosenkranz approximation by means of a multispectrum fitting approach developed at DLR This enables high accuracy parameter retrievals to reproduce the spectra down to noise level and we will present the behavior of line widths, shifts, speed-dependence-, collisional narrowing- and line mixing-parameters over this 140 K temperature range. Tran et al. JQSRT 129, 199-203 (2013); JQSRT 134, 104 (2014). Loos et al., 2014; http://doi.org/10.5281/zenodo.11156. Ngo et al. JQSRT 29, 89-100 (2013); JQSRT 134, 105 (2014).

ROVIBRATIONALLY RESOLVED DIRECT PHOTODISSOCIATION THROUGH THE LYMAN AND WERNER TRANSITIONS OF H{sub 2} FOR FUV/X-RAY-IRRADIATED ENVIRONMENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gay, C. D.; Porter, R. L.; Stancil, P. C.

Using ab initio potential curves and dipole transition moments, cross-section calculations were performed for the direct continuum photodissociation of H{sub 2} through the B{sup 1}{Sigma}{sup +}{sub u} <- X{sup 1}{Sigma}{sup +}{sub g} (Lyman) and C{sup 1}{Pi}{sub u} <- X{sup 1}{Sigma}{sup +}{sub g} (Werner) transitions. Partial cross-sections were obtained for wavelengths from 100 A to the dissociation threshold between the upper electronic state and each of the 301 bound rovibrational levels v''J'' within the ground electronic state. The resulting cross-sections are incorporated into three representative classes of interstellar gas models: diffuse clouds, photon-dominated regions, and X-ray-dominated regions (XDRs). The models, whichmore » used the CLOUDY plasma/molecular spectra simulation code, demonstrate that direct photodissociation is comparable to fluorescent dissociation (or spontaneous radiative dissociation, the Solomon process) as an H{sub 2} destruction mechanism in intense far-ultraviolet or X-ray-irradiated gas. In particular, changes in H{sub 2} rotational column densities are found to be as large as 20% in the XDR model with the inclusion of direct photodissociation. The photodestruction rate from some high-lying rovibrational levels can be enhanced by pumping from H Ly{beta} due to a wavelength coincidence with cross-section resonances resulting from quasi-bound levels of the upper electronic states. Given the relatively large size of the photodissociation data set, a strategy is described to create truncated, but reliable, cross-section data consistent with the wavelength resolving power of typical observations.« less

N2 pressure - broadened O3 line widths and strengths near 1129.4 cm-1

NASA Technical Reports Server (NTRS)

Copeland, G. E.; Majorana, L. N.; Harward, C. N.; Steinkamp, R. J.

1982-01-01

A Beer's Law experiment was performed with a tunable diode laser to find the N2 pressure broadening characteristics of a single 03 absorption line at 1129.426 cm for N2 pressures from 10 to 100 torr (O3 pressure = 3.16 torr). SO2 line positions were used for wavelength calibration. Line shapes were interatively fitted to a Lorentz function. Results were delta (HWHM in MHz) = 47.44 (+ or - 5.34) MHz + 1.730 (+ or - 0.088) MHz/torr *p(torr) with sigma = 0.9897. This intercept compares well with the Doppler O3 - O3 broadened (at 3.16 torr) width of 44.52 Hz. This result in a HWHM line width of 0.44 cm atm at 760 torr and 285 K. The line strengths integrated over delta nu = 0.55 cm were found to be N2 pressure dependent.

CO2 and SO2 IR Line Lists for Venus/Mars and Exo-Planet Atmosphere Studies

NASA Astrophysics Data System (ADS)

Huang, X.; Schwenke, D.; Sergey, T. A.; Lee, T. J.

2012-12-01

Atmospheric studies of both solar system planets and extra-solar planets need accurate spectra data input and analysis from planetary missions and astronomical observations. Accurate Infra-Red (IR) line lists of critical species are necessary to determine the physical conditions and compositions of atmospheres. Here we demonstrate an example of how theoretical chemistry can help in this regard. By combining the state-of-the-art ab initio theory, quantum exact rovibrational CI approach, and selected reliable high resolution experimental data, we have successfully generated the most complete and reliable IR line lists for Carbon Dioxide and Sulfur Dioxide (and their isotopologues) with accuracies of 0.01-0.02 cm-1, or ~10 MHz for microwave spectra. Agreement for observed intensities is around 90%. Our approach not only automatically fills in all the missing bands (especially those weaker, difficult bands) below the highest experiment energies, but also safely extrapolates beyond those with still reliable predictions. The reliability and accuracy of our IR line lists have been verified by the most recent experiments. The CO2 line list actually extends to 30,000 cm-1 and J>180. It works for early planets with temperature as high as 1000-2000K. The SO2 line list covers 0 - 14000 cm-1 and J>100. These line lists are expected to facilitate the atmospheric analysis and modeling of both planets (and moons) within our solar system and beyond to extra-solar planets. 32SO2 IR spectra comparison. (top) Ames-296K line list vs. recent experiment; (bottom) Ames-296K fills in the gaps of HITRAN2008 data. 12C16O2 IR Simulation at different temperatures using the latest Ames-296K IR linelist. (Unpublished work by R.S. Freedman, SETI/NASA Ames SST)

Spatially resolved H2 emission from the disk around T Tau N

NASA Astrophysics Data System (ADS)

Gustafsson, M.; Labadie, L.; Herbst, T. M.; Kasper, M.

2008-09-01

Context: Molecular hydrogen is the main constituent of circumstellar disks and could be an important tracer for the evolution and structure of such disks. So far, H2 has only been detected in a few disks and only through spectroscopic observations, resulting in a limited knowledge of the spatial distribution of the H2 emitting gas. Aims: We report the detection of quiescent H2 emission in a spatially resolved ring-like structure within 100 AU of T Tau N. We present evidence to show that the emission most likely arises from shocks in the atmosphere of a nearly face-on disk around T Tau N. Methods: Using high spatial resolution 3D spectroscopic K-band data, we trace the spatial distribution of several H2 NIR rovibrational lines in the vicinity of T Tau N. We examine the structure of the circumstellar material around the star through SED modeling. Then, we use models of shocks and UV+X-ray irradiation to reproduce the H2 line flux and line ratios in order to test how the H2 is excited. Results: We detect weak H2 emission from the v=1{-}0 S(0), S(1), Q(1) lines and the v=2{-}1 S(1) line in a ring-like structure around T Tau N between 0.1 arcsec ( 15 AU) and 0.7 arcsec ( 100 AU) from the star. The v=1{-}0 S(0) and v=2{-}1 S(1) lines are detected only in the outer parts of the ring structure. Closer to the star, the strong continuum limits our sensitivity to these lines. The total flux of the v=1{-}0 S(1) line is 1.8 × 10-14 erg s-1 cm-2, similar to previous measurements of H2 in circumstellar disks. The velocity of the H2 emitting gas around T Tau N is consistent with the rest velocity of the star, and the H2 does not seem to be part of a collimated outflow. Both shocks impinging on the surface of a disk and irradiation of a disk by UV-photons and X-rays from the central star are plausible candidates for the H2 excitation mechanism. However, irradiation should not create a large degree of excitation at radii larger than 20 AU. Most likely the H2 emission arises in the

Absolute frequencies of water lines near 790 nm with 10-11 accuracy

NASA Astrophysics Data System (ADS)

Chen, J.; Hua, T.-P.; Tao, L.-G.; Sun, Y. R.; Liu, A.-W.; Hu, S.-M.

2018-01-01

Water lines in the infrared are convenient frequency references. We present absolute positions of several H216O ro-vibrational transitions around 790 nm using comb-locked cavity ring-down saturation spectroscopy. Lamb dips of 6 water lines with saturation power in the range of 70-130 kW/cm2 were observed and the line positions were determined with an accuracy of 25 kHz, corresponding to a fractional uncertainty of 6.6 × 10-11. The present work demonstrates the capability to considerably improve the accuracy of the water line positions in the infrared.

Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods.

PubMed

Dalbouha, S; Senent, M L; Komiha, N; Domínguez-Gómez, R

2016-09-28

Various astrophysical relevant molecules obeying the empirical formula C 2 H 3 NO are characterized using explicitly correlated coupled cluster methods (CCSD(T)-F12). Rotational and rovibrational parameters are provided for four isomers: methyl isocyanate (CH 3 NCO), methyl cyanate (CH 3 OCN), methyl fulminate (CH 3 ONC), and acetonitrile N-oxide (CH 3 CNO). A CH 3 CON transition state is inspected. A variational procedure is employed to explore the far infrared region because some species present non-rigidity. Second order perturbation theory is used for the determination of anharmonic frequencies, rovibrational constants, and to predict Fermi resonances. Three species, methyl cyanate, methyl fulminate, and CH 3 CON, show a unique methyl torsion hindered by energy barriers. In methyl isocyanate, the methyl group barrier is so low that the internal top can be considered a free rotor. On the other hand, acetonitrile N-oxide presents a linear skeleton, C 3v symmetry, and free internal rotation. Its equilibrium geometry depends strongly on electron correlation. The remaining isomers present a bend skeleton. Divergences between theoretical rotational constants and previous parameters fitted from observed lines for methyl isocyanate are discussed on the basis of the relevant rovibrational interaction and the quasi-linearity of the molecular skeleton.

Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods

NASA Astrophysics Data System (ADS)

Dalbouha, S.; Senent, M. L.; Komiha, N.; Domínguez-Gómez, R.

2016-09-01

Various astrophysical relevant molecules obeying the empirical formula C2H3NO are characterized using explicitly correlated coupled cluster methods (CCSD(T)-F12). Rotational and rovibrational parameters are provided for four isomers: methyl isocyanate (CH3NCO), methyl cyanate (CH3OCN), methyl fulminate (CH3ONC), and acetonitrile N-oxide (CH3CNO). A CH3CON transition state is inspected. A variational procedure is employed to explore the far infrared region because some species present non-rigidity. Second order perturbation theory is used for the determination of anharmonic frequencies, rovibrational constants, and to predict Fermi resonances. Three species, methyl cyanate, methyl fulminate, and CH3CON, show a unique methyl torsion hindered by energy barriers. In methyl isocyanate, the methyl group barrier is so low that the internal top can be considered a free rotor. On the other hand, acetonitrile N-oxide presents a linear skeleton, C3v symmetry, and free internal rotation. Its equilibrium geometry depends strongly on electron correlation. The remaining isomers present a bend skeleton. Divergences between theoretical rotational constants and previous parameters fitted from observed lines for methyl isocyanate are discussed on the basis of the relevant rovibrational interaction and the quasi-linearity of the molecular skeleton.

An exact variational method to calculate rovibrational spectra of polyatomic molecules with large amplitude motion

NASA Astrophysics Data System (ADS)

Yu, Hua-Gen

2016-08-01

We report a new full-dimensional variational algorithm to calculate rovibrational spectra of polyatomic molecules using an exact quantum mechanical Hamiltonian. The rovibrational Hamiltonian of system is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame. It is expressed in an explicitly Hermitian form. The Hamiltonian has a universal formulation regardless of the choice of orthogonal polyspherical coordinates and the number of atoms in molecule, which is suitable for developing a general program to study the spectra of many polyatomic systems. An efficient coupled-state approach is also proposed to solve the eigenvalue problem of the Hamiltonian using a multi-layer Lanczos iterative diagonalization approach via a set of direct product basis set in three coordinate groups: radial coordinates, angular variables, and overall rotational angles. A simple set of symmetric top rotational functions is used for the overall rotation whereas a potential-optimized discrete variable representation method is employed in radial coordinates. A set of contracted vibrationally diabatic basis functions is adopted in internal angular variables. Those diabatic functions are first computed using a neural network iterative diagonalization method based on a reduced-dimension Hamiltonian but only once. The final rovibrational energies are computed using a modified Lanczos method for a given total angular momentum J, which is usually fast. Two numerical applications to CH4 and H2CO are given, together with a comparison with previous results.

An exact variational method to calculate rovibrational spectra of polyatomic molecules with large amplitude motion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Hua-Gen, E-mail: hgy@bnl.gov

We report a new full-dimensional variational algorithm to calculate rovibrational spectra of polyatomic molecules using an exact quantum mechanical Hamiltonian. The rovibrational Hamiltonian of system is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame. It is expressed in an explicitly Hermitian form. The Hamiltonian has a universal formulation regardless of the choice of orthogonal polyspherical coordinates and the number of atoms in molecule, which is suitable for developing a general program to study the spectra of many polyatomic systems. An efficient coupled-state approach is also proposed to solve the eigenvalue problem of the Hamiltonian using amore » multi-layer Lanczos iterative diagonalization approach via a set of direct product basis set in three coordinate groups: radial coordinates, angular variables, and overall rotational angles. A simple set of symmetric top rotational functions is used for the overall rotation whereas a potential-optimized discrete variable representation method is employed in radial coordinates. A set of contracted vibrationally diabatic basis functions is adopted in internal angular variables. Those diabatic functions are first computed using a neural network iterative diagonalization method based on a reduced-dimension Hamiltonian but only once. The final rovibrational energies are computed using a modified Lanczos method for a given total angular momentum J, which is usually fast. Two numerical applications to CH{sub 4} and H{sub 2}CO are given, together with a comparison with previous results.« less

Infrared spectra and anharmonic coupling of proton-bound nitrogen dimers N2-H+-N2, N2-D+-N2, and 15N2-H+-15N2 in solid para-hydrogen.

PubMed

Liao, Hsin-Yi; Tsuge, Masashi; Tan, Jake A; Kuo, Jer-Lai; Lee, Yuan-Pern

2017-08-09

The proton-bound nitrogen dimer, N 2 -H + -N 2 , and its isotopologues were investigated by means of vibrational spectroscopy. These species were produced upon electron bombardment of mixtures of N 2 (or 15 N 2 ) and para-hydrogen (p-H 2 ) or normal-D 2 (n-D 2 ) during deposition at 3.2 K. Reduced-dimension anharmonic vibrational Schrödinger equations were constructed to account for the strong anharmonic effects in these protonated species. The fundamental lines of proton motions in N 2 -H + -N 2 were observed at 715.0 (NH + N antisymmetric stretch, ν 4 ), 1129.6 (NH + N bend, ν 6 ), and 2352.7 (antisymmetric NN/NN stretch, ν 3 ) cm -1 , in agreement with values of 763, 1144, and 2423 cm -1 predicted with anharmonic calculations using the discrete-variable representation (DVR) method at the CCSD/aug-cc-pVDZ level. The lines at 1030.2 and 1395.5 cm -1 were assigned to combination bands involving nν 2 + ν 4 (n = 1 and 2) according to theoretical calculations; ν 2 is the N 2 N 2 stretching mode. For 15 N 2 -H + - 15 N 2 in solid p-H 2 , the corresponding major lines were observed at 710.0 (ν 4 ), 1016.7 (ν 2 + ν 4 ), 1124.3 (ν 6 ), 1384.8 (2ν 2 + ν 4 ), and 2274.9 (ν 3 ) cm -1 . For N 2 -D + -N 2 in solid n-D 2 , the corresponding major lines were observed at 494.0 (ν 4 ), 840.7 (ν 2 + ν 4 ), 825.5 (ν 6 ), and 2356.2 (ν 3 ) cm -1 . In addition, two lines at 762.0 (weak) and 808.3 cm -1 were tentatively assigned to be some modes of N 2 -H + -N 2 perturbed or activated by a third N 2 near the proton.

An accurate global potential energy surface, dipole moment surface, and rovibrational frequencies for NH3

NASA Astrophysics Data System (ADS)

Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

2008-12-01

A global potential energy surface (PES) that includes short and long range terms has been determined for the NH3 molecule. The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations and the internally contracted averaged coupled-pair functional electronic structure methods have been used in conjunction with very large correlation-consistent basis sets, including diffuse functions. Extrapolation to the one-particle basis set limit was performed and core correlation and scalar relativistic contributions were included directly, while the diagonal Born-Oppenheimer correction was added. Our best purely ab initio PES, denoted "mixed," is constructed from two PESs which differ in whether the ic-ACPF higher-order correlation correction was added or not. Rovibrational transition energies computed from the mixed PES agree well with experiment and the best previous theoretical studies, but most importantly the quality does not deteriorate even up to 10300cm-1 above the zero-point energy (ZPE). The mixed PES was improved further by empirical refinement using the most reliable J =0-2 rovibrational transitions in the HITRAN 2004 database. Agreement between high-resolution experiment and rovibrational transition energies computed from our refined PES for J =0-6 is excellent. Indeed, the root mean square (rms) error for 13 HITRAN 2004 bands for J =0-2 is 0.023cm-1 and that for each band is always ⩽0.06cm-1. For J =3-5 the rms error is always ⩽0.15cm-1. This agreement means that transition energies computed with our refined PES should be useful in the assignment of new high-resolution NH3 spectra and in correcting mistakes in previous assignments. Ideas for further improvements to our refined PES and for extension to other isotopolog are discussed.

High-Level, First-Principles, Full-Dimensional Quantum Calculation of the Ro-vibrational Spectrum of the Simplest Criegee Intermediate (CH2OO).

PubMed

Li, Jun; Carter, Stuart; Bowman, Joel M; Dawes, Richard; Xie, Daiqian; Guo, Hua

2014-07-03

The ro-vibrational spectrum of the simplest Criegee intermediate (CH2OO) has been determined quantum mechanically based on nine-dimensional potential energy and dipole surfaces for its ground electronic state. The potential energy surface is fitted to more than 50 000 high-level ab initio points with a root-mean-square error of 25 cm(-1), using a recently proposed permutation invariant polynomial neural network method. The calculated rotational constants, vibrational frequencies, and spectral intensities of CH2OO are in excellent agreement with experiment. The potential energy surface provides a valuable platform for studying highly excited vibrational and unimolecular reaction dynamics of this important molecule.

Consensus Assignments for Water Vapor Lines Not Assigned on the HITRAN Database: 13,200 to 16,500/cm

NASA Technical Reports Server (NTRS)

Giver, Lawerence P.; Chackerian, Charles, Jr.; Freedman, Richard S.; Varanasi, Prasad; Gore, Warren (Technical Monitor)

2000-01-01

There are nearly 800 water Vapor-lines in the 13,200-16,500/cm region that do not have rovibrational assignments in the HITRAN database. The positions and intensities in the database were determined by Mandin et al., but assignments could not be determined at that time. Polyansky, et al. have now assigned over 600 of the unassigned lines in the 11,200-16,500/cm region. Schwenke has also given rovibrational assignments to many of these unassigned lines throughout the visible and near-infrared. Both articles changed the assignments of some HITRAN lines. Carleer et al. extend assignments to some weaker lines measured by them on new spectra with excellent signal/noise. However, some lines measured by Mandin et al. were omitted by Carleer, et al. because of blends due to lower spectral resolution. The rovibrational assignments of Polyansky et al. completely agree with those in Schwenke's article for only about 200 lines. However, Schwenke's ab initio line list is available on his internet site (http://ccf.arc.nasa.gov/-dschwenke). A detailed comparison of the Polyansky et al.line list, the Carleer et al.line list, and Schwenke's ab initio line list shows a larger number of agreements. In many cases the disagreement is only about the vibrational and/or rotational upper level, while there is agreement on the lower state assignment and energy level, "E", which is of primary importance for atmospheric applications. We will present a line list of "consensus" assignments in the 13,200-16,500/cm region for consideration of inclusion on the HITRAN and GEISA databases. This will substantially reduce the number of unassigned lines on the databases in this spectral region.

Nonequilibrium shock-heated nitrogen flows using a rovibrational state-to-state method

NASA Astrophysics Data System (ADS)

Panesi, M.; Munafò, A.; Magin, T. E.; Jaffe, R. L.

2014-07-01

A rovibrational collisional model is developed to study the internal energy excitation and dissociation processes behind a strong shock wave in a nitrogen flow. The reaction rate coefficients are obtained from the ab initio database of the NASA Ames Research Center. The master equation is coupled with a one-dimensional flow solver to study the nonequilibrium phenomena encountered in the gas during a hyperbolic reentry into Earth's atmosphere. The analysis of the populations of the rovibrational levels demonstrates how rotational and vibrational relaxation proceed at the same rate. This contrasts with the common misconception that translational and rotational relaxation occur concurrently. A significant part of the relaxation process occurs in non-quasi-steady-state conditions. Exchange processes are found to have a significant impact on the relaxation of the gas, while predissociation has a negligible effect. The results obtained by means of the full rovibrational collisional model are used to assess the validity of reduced order models (vibrational collisional and multitemperature) which are based on the same kinetic database. It is found that thermalization and dissociation are drastically overestimated by the reduced order models. The reasons of the failure differ in the two cases. In the vibrational collisional model the overestimation of the dissociation is a consequence of the assumption of equilibrium between the rotational energy and the translational energy. The multitemperature model fails to predict the correct thermochemical relaxation due to the failure of the quasi-steady-state assumption, used to derive the phenomenological rate coefficient for dissociation.

Rovibrational Constants for the ν 6 and 2ν 9 Bands of HCOOD by Fourier Transform Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Tan, T. L.; Goh, K. L.; Ong, P. P.; Teo, H. H.

1999-11-01

The Fourier transform infrared spectrum of the ν6 and 2ν9 bands of deuterated formic acid (HCOOD) was recorded with an apodized resolution of 0.004 cm-1 in the frequency range of 930-1040 cm-1. These two bands with band centers 40 cm-1 apart were mutually coupled by Coriolis and Fermi interactions. By fitting a total of 1076 infrared transitions of both ν6 and 2ν9 with a standard deviation of 0.00075 cm-1 using a Watson's A-reduced Hamiltonian in the Ir representation with the inclusion of c-type Coriolis and a Fermi-resonance term, two sets of rovibrational constants for v6 = 1, and v9 = 2 states were derived for the first time. Both ν6 and 2ν9 bands are A type with band centers at 972.8520 ± 0.0001 and 1011.6766 ± 0.0001 cm-1, respectively.

Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mátyus, Edit, E-mail: matyus@chem.elte.hu; Szidarovszky, Tamás; Császár, Attila G., E-mail: csaszar@chem.elte.hu

2014-10-21

Introducing different rotational and vibrational masses in the nuclear-motion Hamiltonian is a simple phenomenological way to model rovibrational non-adiabaticity. It is shown on the example of the molecular ion H{sub 3}{sup +}, for which a global adiabatic potential energy surface accurate to better than 0.1 cm{sup −1} exists [M. Pavanello, L. Adamowicz, A. Alijah, N. F. Zobov, I. I. Mizus, O. L. Polyansky, J. Tennyson, T. Szidarovszky, A. G. Császár, M. Berg et al., Phys. Rev. Lett. 108, 023002 (2012)], that the motion-dependent mass concept yields much more accurate rovibrational energy levels but, unusually, the results are dependent upon themore » choice of the embedding of the molecule-fixed frame. Correct degeneracies and an improved agreement with experimental data are obtained if an Eckart embedding corresponding to a reference structure of D{sub 3h} point-group symmetry is employed. The vibrational mass of the proton in H{sub 3}{sup +} is optimized by minimizing the root-mean-square (rms) deviation between the computed and recent high-accuracy experimental transitions. The best vibrational mass obtained is larger than the nuclear mass of the proton by approximately one third of an electron mass, m{sub opt,p}{sup (v)}=m{sub nuc,p}+0.31224 m{sub e}. This optimized vibrational mass, along with a nuclear rotational mass, reduces the rms deviation of the experimental and computed rovibrational transitions by an order of magnitude. Finally, it is shown that an extension of the algorithm allowing the use of motion-dependent masses can deal with coordinate-dependent mass surfaces in the rovibrational Hamiltonian, as well.« less

Electronic structure and rovibrational properties of ZnOH in the X̃²A' electronic state: a computational molecular spectroscopy study.

PubMed

Hirano, Tsuneo; Andaloussi, Mounir Ben Dahman; Nagashima, Umpei; Jensen, Per

2014-09-07

The three-dimensional ground-state potential energy surface of ZnOH has been calculated ab initio at the MR-SDCI+Q_DK3/[QZP ANO-RCC (Zn, O, H)] level of theory and used as basis for a study of the rovibrational properties carried out by means of the program MORBID (Morse Oscillator Rigid Bender Internal Dynamics). The electronic ground state is  (2)A' (correlating with (2)Σ(+) at the linear configuration). The equilibrium structure has r(e)(Zn-O) = 1.8028 Å, r(e)(O-H) = 0.9606 Å, and ∠e(Zn-O-H) = 114.9°. The Zn-O bond is essentially ionic, with appreciable covalency. The bonding character is compared with those of FeOH (quasi-linear) and CsOH (linear). The rovibrationally averaged structural parameters, determined as expectation values over MORBID wavefunctions, are ⟨r(Zn-O)⟩0 = 1.8078 Å, ⟨r(O-H)⟩0 = 0.9778 Å, and ⟨∠(Zn-O-H)⟩0 = 117°. The Yamada-Winnewisser quasi-linearity parameter is found to be γ0 = 0.84, which is close to 1.0 as expected for a bent molecule. Since no experimental rovibrational spectrum has been reported thus far, this spectrum has been simulated from the ab initio potential energy and dipole moment surfaces. The amphoteric character of ZnOH is also discussed.

First laboratory detection of an absorption line of the first overtone electric quadrupolar band of N2 by CRDS near 2.2 μm

NASA Astrophysics Data System (ADS)

Čermák, P.; Vasilchenko, S.; Mondelain, D.; Kassi, S.; Campargue, A.

2017-01-01

The extremely weak 2-0 O(14) electric quadrupole transition of N2 has been detected by very high sensitivity Cavity Ring Down spectroscopy near 4518 cm-1. It is the first N2 absorption line in the first overtone band reported so far from laboratory experiments. By combining a feedback narrowed Distributed Feedback laser diode with a passive cell tracking technique, a limit of detection of αmin ∼ 1.2 × 10-11 cm-1 was achieved after one day of spectra averaging. The N2 2-0 O(14) line position and line intensity (about 1.5 × 10-30 cm/molecule) agree with calculated values provided in the HITRAN2012 database.

Rotation of molecular hydrogen in Si: unambiguous identification of ortho-H(2) and para-D(2).

PubMed

Chen, E Elinor; Stavola, Michael; Beall Fowler, W; Zhou, J Anna

2002-06-17

The 3618.4 and 2642.6 cm(-1) infrared absorption lines of interstitial H(2) and D(2) in silicon have been studied under applied uniaxial stresses. The resulting splittings and their small dependence on isotope establish that H(2) in Si is a nearly free rotor and that these lines arise from vibrational transitions between rovibrational states with rotational quantum number J = 1 (T(2) in T(d) symmetry) for ortho-H(2) and para-D(2).

New Line Lists for planetological applications: HC3N and C4H2

NASA Astrophysics Data System (ADS)

Jolly, A.; Benilan, Y.; Fayt, A.

2009-04-01

The Composite Infrared Spectrometer (CIRS) on-board Cassini, after four years of operation in Saturnian orbit with over thirty close fly-bys of Titan, has obtained spectra in the far and mid-infrared with a spectral resolution of 0.5 cm-1. Mismatch between observed spectra and model spectra obtained from the available line lists has led us to study the bending bands of HC3N and C4H2, the longest carbon chains observed on Titan. Our experimental study for HC3N (Jolly et al. 2007, J.Mol.Spec) has shown that band intensities had to be revised and that including hot bands with lower level as high as 1300 cm-1 was necessary to model our experimental spectra at 0.5 cm-1 resolution. A new extended line list could be obtained by fitting high resolution data with the help of a global analysis. This line list was made available to the astronomers of the CIRS team and will be included in the next version of the GEISA data base. Thanks to the precision of the new spectroscopic data, 13C isotopologues of HC3N have been detected and quantified for the first time in the atmosphere of Titan (Jennings et al. 2008, ApJL). Search for the 15N isotopologues of HC3N will also be presented. The proportion of hot bands is even more important for C4H2 than for HC3N and a new extended line list was absolutely necessary to improve the CIRS spectral analysis. We will present a new line list and show comparison between synthetic spectra and experimental spectra of C4H2 obtained between 193 and 296 K at 0.1 and 0.5 cm-1 resolution. Comparison of model spectra to CIRS observations of C4H2 at 220 and 630 cm-1 will also be presented. Detections of hot bands and isotopes in cold environments such as Titan will be emphasized.

Observations of Infrared Molecular Lines Toward the Massive Protostar GL 2591

NASA Astrophysics Data System (ADS)

Knez, C.; Boonman, A. M. S.; Lacy, J. H.; Evans, N. J., II; Richter, M. J.

2001-12-01

Using TEXES (Texas Echelon Cross Echelle Spectrograph) at the NASA Infrared Telescope Facility, we have observed rovibrational transitions of C2H2 and HCN near 13 microns in absorption toward the deeply embedded, massive protostar, GL 2591. GL 2591 is obscured by about 70 magnitudes of visual extinction; however, it is one of the brightest mid-infrared sources. The following lines were observed: C2H2 R(5), R(6), R(12), and R(13) and HCN R(10) and R(16). With a spectral resolution of ~ 3 km/s, all lines are resolved. We show the line profiles and compare the spectra to previous results from Carr et al. (1995), Lahuis & van Dishoeck (2000) and Boonman et al. (2001). Observations with TEXES were supported by the Texas Advanced Research Program.

Frequency metrology of the acetylene lines near 789 nm from lamb-dip measurements

NASA Astrophysics Data System (ADS)

Tao, Lei-Gang; Hua, Tian-Peng; Sun, Yu R.; Wang, Jin; Liu, An-Wen; Hu, Shui-Ming

2018-05-01

Lamb-dips of the ro-vibrational lines of 12C2H2 near 789 nm were recorded using cavity ring-down saturation spectroscopy. Calibrated by an optical frequency comb, frequencies of 45 acetylene lines were determined with an accuracy of 1.1 ×10-7 cm-1 (δν / ν = 8 ×10-12), which is over two orders of magnitude more accurate than previous Doppler-limited studies. An averaged shift of about 0.01 cm-1 were found by comparing the upper energies obtained in this work to those recently presented by Chubb et al. from a MARVEL analysis.

High-resolution spectroscopy and global analysis of CF4 rovibrational bands to model its atmospheric absorption

NASA Astrophysics Data System (ADS)

Carlos, M.; Gruson, O.; Richard, C.; Boudon, V.; Rotger, M.; Thomas, X.; Maul, C.; Sydow, C.; Domanskaya, A.; Georges, R.; Soulard, P.; Pirali, O.; Goubet, M.; Asselin, P.; Huet, T. R.

2017-11-01

CF4, or tetrafluoromethane, is a chemically inert and strongly absorbing greenhouse gas, mainly of anthropogenic origin. In order to monitor and reduce its atmospheric emissions and concentration, it is thus necessary to obtain an accurate model of its infrared absorption. Such models allow opacity calculations for radiative transfer atmospheric models. In the present work, we perform a global analysis (divided into two distinct fitting schemes) of 17 rovibrational bands of CF4. This gives a reliable model of many of its lower rovibrational levels and allows the calculation of the infrared absorption in the strongly absorbing ν3 region (1283 cm-1 / 7.8 μm), including the main hot band, namely ν3 +ν2 -ν2 as well as ν3 +ν1 -ν1 ; we could also extrapolate the ν3 +ν4 -ν4 absorption. This represents almost 92% of the absorption at room temperature in this spectral region. A new accurate value of the C-F bond length is evaluated to re = 1.314860(21) Å. The present results have been used to update the HITRAN, GEISA and TFMeCaSDa (VAMDC) databases.

The Fundamental Quadrupole Band of (14)N2: Line Positions from High-Resolution Stratospheric Solar Absorption Spectra

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Zander, R.; Goldman, A.; Murcray, F. J.; Murcray, D. G.; Grunson, M. R.; Farmer, C. B.

1991-01-01

The purpose of this note is to report accurate measurements of the positions of O- and S-branch lines of the (1-0) vibration-rotation quadrupole band of molecular nitrogen ((14)N2) and improved Dunham coefficients derived from a simultaneous least-squares analysis of these measurements and selected infrared and far infrared data taken from the literature. The new measurements have been derived from stratospheric solar occultation spectra recorded with Fourier transform spectrometer (FTS) instruments operated at unapodized spectral resolutions of 0.002 and 0.01 /cm. The motivation for the present investigation is the need for improved N2 line parameters for use in IR atmospheric remote sensing investigations. The S branch of the N2 (1-0) quadrupole band is ideal for calibrating the line-of-sight airmasses of atmospheric spectra since the strongest lines are well placed in an atmospheric window, their absorption is relatively insensitive to temperature and is moderately strong (typical line center depths of 10 to 50% in high-resolution ground-based solar spectra and in lower stratospheric solar occultation spectra), and the volume mixing ratio of nitrogen is constant in the atmosphere and well known. However, a recent investigation has'shown the need to improve the accuracies of the N2 fine positions, intensities, air-broadened half-widths, and their temperature dependences to fully exploit this calibration capability (1). The present investigation addresses the problem of improving the accuracy of the N2 line positions.

Potential energy surface and quantum dynamics study of rovibrational states for HO(3) (X (2)A'').

PubMed

Braams, Bastiaan J; Yu, Hua-Gen

2008-06-07

An analytic potential energy surface has been constructed by fitting to about 28 thousand energy points for the electronic ground-state (X (2)A'') of HO(3). The energy points are calculated using a hybrid density functional HCTH and a large basis set aug-cc-pVTZ, i.e., a HCTH/aug-cc-pVTZ density functional theory (DFT) method. The DFT calculations show that the trans-HO(3) isomer is the global minimum with a potential well depth of 9.94 kcal mol(-1) with respect to the OH + O(2) asymptote. The equilibrium geometry of the cis-HO(3) conformer is located 1.08 kcal mol(-1) above that of the trans-HO(3) one with an isomerization barrier of 2.41 kcal mol(-1) from trans- to cis-HO(3). By using this surface, a rigorous quantum dynamics (QD) study has been carried out for computing the rovibrational energy levels of HO(3). The calculated results determine a dissociation energy of 6.15 kcal mol(-1), which is in excellent agreement with the experimental value of Lester et al. [J. Phys. Chem. A, 2007, 111, 4727.].

Uncertainties Associated with Theoretically Calculated N2-Broadened Half-Widths of H2O Lines

NASA Technical Reports Server (NTRS)

Ma, Q.; Tipping, R. H.; Gamache, R. R.

2010-01-01

With different choices of the cut-offs used in theoretical calculations, we have carried out extensive numerical calculations of the N2-broadend Lorentzian half-widths of the H2O lines using the modified Robert-Bonamy formalism. Based on these results, we are able to thoroughly check for convergence. We find that, with the low-order cut-offs commonly used in the literature, one is able to obtain converged values only for lines with large half-widths. Conversely, for lines with small half-widths, much higher cut-offs are necessary to guarantee convergence. We also analyse the uncertainties associated with calculated half-widths, and these are correlated as above. In general, the smaller the half-widths, the poorer the convergence and the larger the uncertainty associated with them. For convenience, one can divide all H2O lines into three categories, large, intermediate, and small, according to their half-width values. One can use this division to judge whether the calculated half-widths are converged or not, based on the cut-offs used, and also to estimate how large their uncertainties are. We conclude that with the current Robert- Bonamy formalism, for lines in category lone can achieve the accuracy requirement set by HITRAN, whereas for lines in category 3, it 'is impossible to meet this goal.

N=2 supersymmetric quantum mechanics of N Lieb-Liniger-Yang bosons on a line

NASA Astrophysics Data System (ADS)

Mateos Guilarte, J.; Moreno Mosquera, A.

2017-02-01

A supersymmetric generalization of the Lieb-Liniger-Yang dynamics governing N massive bosons moving on a line with delta interactions among them at coinciding points is developed. The analysis of the delicate balance between integrability and-supersymmetry, starting from the exactly solvable non-supersymmetric LLY system, is one of the paper main concerns. Two extreme regimes of the N parameter are explored: 1) For few bosons we fall in the realm of supersymmetric quantum mechanics with a short number of degrees of freedom, e.g., the SUSY Pösch-Teller potentials if N = 1 . 2) For large N we deal with supersymmetric extensions of many-body systems in the thermodynamic limit akin, e.g., to the supersymmetric Calogero-Sutherland systems. Emphasis will be put in the investigation of the ground-state structure of these quantum mechanical systems enjoying {N}=2 extended supersymmetry without spoiling integrability. The decision about wether or not supersymmetry is spontaneously broken, a central question in SUSY quantum mechanics determined from the ground-state structure, is another goal of the paper.

Line Lists for LiF and LiCl in the X 1Σ+ Ground State

NASA Astrophysics Data System (ADS)

Bittner, Dror M.; Bernath, Peter F.

2018-03-01

Vibration–rotation line lists for 6LiF, 7LiF, 6Li35Cl, 6Li37Cl, 7Li35Cl, and 7Li37Cl in the X 1Σ+ ground states have been prepared. The rovibrational energy levels have been calculated using potential energy surfaces determined by direct potential-fitting employing the rotational and rovibrational transition frequencies of all isotopologues, and required the inclusion of Born–Oppenheimer breakdown terms. Dipole moment functions calculated ab initio at the MRCI/aug-cc-pwCV5Z level have been used for line strength calculations. Partition functions for temperatures up to 5000 K have been calculated. LiF and LiCl are predicted to be present in the atmospheres of hot rocky exoplanets, brown dwarfs, and cool stars.

Prospects for transferring 87Rb84Sr dimers to the rovibrational ground state based on calculated molecular structures

NASA Astrophysics Data System (ADS)

Chen, Tao; Zhu, Shaobing; Li, Xiaolin; Qian, Jun; Wang, Yuzhu

2014-06-01

Using fitted model potential curves of the ground and lowest three excited states yielded by the relativistic Kramers-restricted multireference configuration interaction method with 19 electrons correlated, we theoretically investigate the rovibrational properties including the number of vibrational state and diagonally distributed Franck-Condon factors for a 87Rb84Sr molecule. Benefiting from a turning point at about v'=20 for the Franck-Condon factors between the ground state and spin-orbit 2(Ω=1/2) excited state, we choose |2(Ω=1/2),v'=21,J'=1> as the intermediate state in the three-level model to theoretically analyze the possibility of performing stimulated Raman adiabatic passage to transfer weakly bound RbSr molecules to the rovibrational ground state. With 1550 nm pump laser (2 W/cm2) and 1342 nm dump laser (10 mW/cm2) employed and appropriate settings of pulse time length (about 300 μs), we have formalistically achieved a round-trip transfer efficiency of 60%, namely 77% for one-way transfer. The results demonstrate the possibility of producing polar 87Rb84Sr molecules efficiently in a submicrokelvin regime, and further provide promising directions for future theoretical and experimental studies on alkali-alkaline(rare)-earth dimers.

High Accuracy Potential Energy Surface, Dipole Moment Surface, Rovibrational Energies and Line List Calculations for ^{14}NH_3

NASA Astrophysics Data System (ADS)

Coles, Phillip; Yurchenko, Sergei N.; Polyansky, Oleg; Kyuberis, Aleksandra; Ovsyannikov, Roman I.; Zobov, Nikolay Fedorovich; Tennyson, Jonathan

2017-06-01

We present a new spectroscopic potential energy surface (PES) for ^{14}NH_3, produced by refining a high accuracy ab initio PES to experimental energy levels taken predominantly from MARVEL. The PES reproduces 1722 matched J=0-8 experimental energies with a root-mean-square error of 0.035 cm-1 under 6000 cm^{-1} and 0.059 under 7200 cm^{-1}. In conjunction with a new DMS calculated using multi reference configuration interaction (MRCI) and H=aug-cc-pVQZ, N=aug-cc-pWCVQZ basis sets, an infrared (IR) line list has been computed which is suitable for use up to 2000 K. The line list is used to assign experimental lines in the 7500 - 10,500 cm^{-1} region and previously unassigned lines in HITRAN in the 6000-7000 cm^{-1} region. Oleg L. Polyansky, Roman I. Ovsyannikov, Aleksandra A. Kyuberis, Lorenzo Lodi, Jonathan Tennyson, Andrey Yachmenev, Sergei N. Yurchenko, Nikolai F. Zobov, J. Mol. Spec., 327 (2016) 21-30 Afaf R. Al Derzia, Tibor Furtenbacher, Jonathan Tennyson, Sergei N. Yurchenko, Attila G. Császár, J. Quant. Spectrosc. Rad. Trans., 161 (2015) 117-130

Ab initio-informed maximum entropy modeling of rovibrational relaxation and state-specific dissociation with application to the O2 + O system

NASA Astrophysics Data System (ADS)

Kulakhmetov, Marat; Gallis, Michael; Alexeenko, Alina

2016-05-01

Quasi-classical trajectory (QCT) calculations are used to study state-specific ro-vibrational energy exchange and dissociation in the O2 + O system. Atom-diatom collisions with energy between 0.1 and 20 eV are calculated with a double many body expansion potential energy surface by Varandas and Pais [Mol. Phys. 65, 843 (1988)]. Inelastic collisions favor mono-quantum vibrational transitions at translational energies above 1.3 eV although multi-quantum transitions are also important. Post-collision vibrational favoring decreases first exponentially and then linearly as Δv increases. Vibrationally elastic collisions (Δv = 0) favor small ΔJ transitions while vibrationally inelastic collisions have equilibrium post-collision rotational distributions. Dissociation exhibits both vibrational and rotational favoring. New vibrational-translational (VT), vibrational-rotational-translational (VRT) energy exchange, and dissociation models are developed based on QCT observations and maximum entropy considerations. Full set of parameters for state-to-state modeling of oxygen is presented. The VT energy exchange model describes 22 000 state-to-state vibrational cross sections using 11 parameters and reproduces vibrational relaxation rates within 30% in the 2500-20 000 K temperature range. The VRT model captures 80 × 106 state-to-state ro-vibrational cross sections using 19 parameters and reproduces vibrational relaxation rates within 60% in the 5000-15 000 K temperature range. The developed dissociation model reproduces state-specific and equilibrium dissociation rates within 25% using just 48 parameters. The maximum entropy framework makes it feasible to upscale ab initio simulation to full nonequilibrium flow calculations.

Critical evaluation of measured rotational-vibrational transitions of four sulphur isotopologues of S16O2

NASA Astrophysics Data System (ADS)

Tóbiás, Roland; Furtenbacher, Tibor; Császár, Attila G.; Naumenko, Olga V.; Tennyson, Jonathan; Flaud, Jean-Marie; Kumar, Praveen; Poirier, Bill

2018-03-01

A critical evaluation and validation of the complete set of previously published experimental rotational-vibrational line positions is reported for the four stable sulphur isotopologues of the semirigid SO2 molecule - i.e., 32S16O2, 33S16O2, 34S16O2, and 36S16O2. The experimentally measured, assigned, and labeled transitions are collated from 43 sources. The 32S16O2, 33S16O2, 34S16O2, and 36S16O2 datasets contain 40,269, 15,628, 31,080, and 31 lines, respectively. Of the datasets collated, only the extremely limited 36S16O2 dataset is not subjected to a detailed analysis. As part of a detailed analysis of the experimental spectroscopic networks corresponding to the ground electronic states of the 32S16O2, 33S16O2, and 34S16O2 isotopologues, the MARVEL (Measured Active Rotational-Vibrational Energy Levels) procedure is used to determine the rovibrational energy levels. The rovibrational levels and their vibrational parent and asymmetric-top quantum numbers are compared to ones obtained from accurate variational nuclear-motion computations as well as to results of carefully designed effective Hamiltonian models. The rovibrational energy levels of the three isotopologues having the same labels are also compared against each other to ensure self-consistency. This careful, multifaceted analysis gives rise to 15,130, 5852, and 10,893 validated rovibrational energy levels, with a typical accuracy of a few 0.0001 cm-1 , for 32S16O2, 33S16O2, and 34S16O2, respectively. The extensive list of validated experimental lines and empirical (MARVEL) energy levels of the S16O2 isotopologues studied are deposited in the Supplementary Material of this article, as well as in the distributed information system ReSpecTh (http://respecth.hu).

Fluorescent excitation of Fe 2, Mn 2, Ti 2, N 1 lines by V 4, N 5, O 6: Emission lines in the spectra of symbiotic stars and Seyfert galaxies

NASA Technical Reports Server (NTRS)

Gilra, D. P.

1984-01-01

Analysis of the published IUE and ground based high resolution spectra of symbiotic stars, particularly RR Tel, shows that the dominant excitation mechanism of Fe II, Mn II, Ti II, and N I lines is the selective fluorescent excitation of some levels by the strong C IV, N V, and O VI emission lines. The same mechanism should work for the excitation of Fe II lines in the spectra of Seyfert galaxies and Q60's whose emission spectra are quite similar to those of symbiotic stars. The similarities and differences between the fluroescent excitation mechanism reported herein and the Bowen's mechanism is analyzed.

Collisional Removal of O2 (c(sup 1) Sigma(sup-)(sub u), nu=9) by O2, N2, and He

NASA Technical Reports Server (NTRS)

Copeland, Richard A.; Knutsen, Karen; Onishi, Marc E.; Yalcin, Talat

1996-01-01

The collisional removal Of 02 molecules in selected vibrational levels of the c state is studied using a two-laser double-resonance technique. The output of the first laser excites the 02 to nu = 9 or 10 of the c Sigma - state, and the ultraviolet output of the second laser monitors specific rovibrational levels via resonance-enhanced ionization. The temporal evolution of the c Sigma u state vibrational level is observed by scanning the time delay between the two pulsed lasers. As the rate constants for 02 and N2 are similar in magnitude, N2 collisions dominate the removal rate in the earth's atmosphere. For v= 10 colliding with 02, we find a removal rate constant that is 2-5 times that for v=9 and that single quantum collision cascade is an important pathway for removal.

Using monomer vibrational wavefunctions as contracted basis functions to compute rovibrational levels of an H2O-atom complex in full dimensionality.

PubMed

Wang, Xiao-Gang; Carrington, Tucker

2017-03-14

In this paper, we present new ideas for computing rovibrational energy levels of molecules composed of two components and apply them to H 2 O-Cl - . When both components are themselves molecules, Euler angles that specify their orientation with respect to an axis system attached to the inter-monomer vector are used as vibrational coordinates. For H 2 O-Cl - , there is only one set of Euler angles. Using Euler angles as intermolecular vibrational coordinates is advantageous because in many cases coupling between them and coordinates that describe the shape of the monomers is unimportant. The monomers are not assumed to be rigid. In the most efficient calculation, vibrational wavefunctions of the monomers are used as contracted basis functions. Energy levels are calculated using the Lanczos algorithm.

Using monomer vibrational wavefunctions as contracted basis functions to compute rovibrational levels of an H2O-atom complex in full dimensionality

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2017-03-01

In this paper, we present new ideas for computing rovibrational energy levels of molecules composed of two components and apply them to H2O-Cl-. When both components are themselves molecules, Euler angles that specify their orientation with respect to an axis system attached to the inter-monomer vector are used as vibrational coordinates. For H2O-Cl-, there is only one set of Euler angles. Using Euler angles as intermolecular vibrational coordinates is advantageous because in many cases coupling between them and coordinates that describe the shape of the monomers is unimportant. The monomers are not assumed to be rigid. In the most efficient calculation, vibrational wavefunctions of the monomers are used as contracted basis functions. Energy levels are calculated using the Lanczos algorithm.

Intermolecular configurations dominated by quadrupole-quadrupole electrostatic interactions: explicit correlation treatment of the five-dimensional potential energy surface and infrared spectra for the CO-N2 complex.

PubMed

Liu, Jing-Min; Zhai, Yu; Zhang, Xiao-Long; Li, Hui

2018-01-17

A thorough understanding of the intermolecular configurations of van der Waals complexes is a great challenge due to their weak interactions, floppiness and anharmonic nature. Although high-resolution microwave or infrared spectroscopy provides one of the most direct and precise pieces of experimental evidence, the origin and key role in determining such intermolecular configurations of a van der Waals system strongly depend on its highly accurate potential energy surface (PES) and a detailed analysis of its ro-vibrational wavefunctions. Here, a new five-dimensional potential energy surface for the van der Waals complex of CO-N 2 which explicitly incorporates the dependence on the stretch coordinate of the CO monomer is generated using the explicitly correlated couple cluster (CCSD(T)-F12) method in conjunction with a large basis set. Analytic four-dimensional PESs are obtained by the least-squares fitting of vibrationally averaged interaction energies for v = 0 and v = 1 to the Morse/Long-Range potential mode (V MLR ). These fits to 7966 points have root-mean-square deviations (RMSD) of 0.131 cm -1 and 0.129 cm -1 for v = 0 and v = 1, respectively, with only 315 parameters. Energy decomposition analysis is carried out, and it reveals that the dominant factor in controlling intermolecular configurations is quadrupole-quadrupole electrostatic interactions. Moreover, the rovibrational levels and wave functions are obtained for the first time. The predicted infrared transitions and intensities for the ortho-N 2 -CO complex as well as the calculated energy levels for para-N 2 -CO are in good agreement with the available experimental data with RMSD discrepancies smaller than 0.068 cm -1 . The calculated infrared band origin shift associated with the fundamental band frequency of CO is -0.721 cm -1 for ortho-N 2 -CO which is in excellent agreement with the experimental value of -0.739 cm -1 . The agreement with experimental values validates the high quality of the PESs

A STUDY OF RO-VIBRATIONAL OH EMISSION FROM HERBIG Ae/Be STARS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brittain, Sean D.; Reynolds, Nickalas; Najita, Joan R.

2016-10-20

We present a study of ro-vibrational OH and CO emission from 21 disks around Herbig Ae/Be stars. We find that the OH and CO luminosities are proportional over a wide range of stellar ultraviolet luminosities. The OH and CO line profiles are also similar, indicating that they arise from roughly the same radial region of the disk. The CO and OH emission are both correlated with the far-ultraviolet luminosity of the stars, while the polycyclic aromatic hydrocarbon (PAH) luminosity is correlated with the longer wavelength ultraviolet luminosity of the stars. Although disk flaring affects the PAH luminosity, it is notmore » a factor in the luminosity of the OH and CO emission. These properties are consistent with models of UV-irradiated disk atmospheres. We also find that the transition disks in our sample, which have large optically thin inner regions, have lower OH and CO luminosities than non-transition disk sources with similar ultraviolet luminosities. This result, while tentative given the small sample size, is consistent with the interpretation that transition disks lack a gaseous disk close to the star.« less

The Wardle Instability in Interstellar Shocks. 2; Gas Temperture and Line Emission

NASA Technical Reports Server (NTRS)

Neufeld, David A.; Stone, James M.

1997-01-01

We have modeled the gas temperature structure in unstable C-type shocks and obtained predictions for the resultant CO and H2 rotational line emissions, using numerical simulations of the Wardle instability. Our model for the thermal balance of the gas includes ion-neutral frictional heating; compressional heating; radiative cooling due to rotational and ro-vibrational transitions of the molecules CO, H2O, and H2; and gas-grain collisional cooling. We obtained results for the gas temperature distribution in-and H2 and CO line emission from-shocks of neutral Alfvenic Mach number 10 and velocity 20 or 40 km/ s in which the Wardle instability has saturated. Both two- and three-dimensional simulations were carried out for shocks in which the preshock magnetic field is perpendicular to the shock propagation direction, and a two-dimensional simulation was carried out for the case in which the magnetic field is obliquely oriented with respect to the shock propagation direction. Although the Wardle instability profoundly affects the density structure behind C-type shocks, most of the shock-excited molecular line emission is generated upstream of the region where the strongest effects of the instability are felt. Thus the Wardle instability has a relatively small effect on the overall gas temperature distribution in-and the emission-line spectrum from-C-type shocks, at least for the cases that we have considered. In none of the cases that we have considered thus far did any of the predicted emission-line luminosities change by more than a factor of 2.5, and in most cases the effects of instability were significantly smaller than that. Slightly larger changes in the line luminosities seem likely for three-dimensional simulations of oblique shocks, although such simulations have yet to be carried out and lie beyond the scope of this study. Given the typical uncertainties that are always present when model predictions are compared with real astronomical data, we conclude that

Line mixing in a N2-broadened CO2 Q branch observed with a tunable diode laser

NASA Technical Reports Server (NTRS)

Gentry, Bruce; Strow, L. Larrabee

1987-01-01

Line-mixing effects have been observed in the infrared Q branch of the (11/1/0,03/1/0)I-00/0/0 band of CO2 at 2076/cm. A tunable diode laser spectrometer was used to record spectra of CO2 broadened by N2 and O2 at total pressures ranging from 100 to 720 torr. The observed absorption coefficients are up to 65 percent lower than those calculated using an isolated Lorentzian line approximation. A simple energy gap scaling law is used to determine the off-diagonal relaxation matrix elements from the known pressure-broadening coefficients. The spectra calculated using these matrix elements reproduces the observed absorption coefficients to within several percent.

Molecular Line and Continuum Opacities for Modeling of Extrasolar Giant Planet and Cool Stellar Atmospheres

NASA Technical Reports Server (NTRS)

Weck, P. F.; Schweitzer, A.; Stancil, P. C.; Hauschildt, P. H.; Kirby, K.; Yamaguchi, Y.; Allen, W. D.

2002-01-01

The molecular line and continuum opacities are investigated in the atmospheres of cool stars and Extrasolar Giant Planets (EGPs). Using a combination of ab inito and experimentally derived potential curves and dipole transition moments, accurate data have been calculated for rovibrationally-resolved oscillator strengths and photodissociation cross sections in the B' (sup 2)Sigma+ (left arrow) X (sup 2)Sigma+ and A (sup 2)Pi (left arrow) X (sup 2)Sigma+ band systems in MgH. We also report our progress on the study of the electronic structure of LiCl and FeH.

Stratospheric and mesospheric pressure-temperature profiles from rotational analysis of CO2 lines in atmospheric trace molecule spectroscopy/ATLAS 1 infrared solar occultation spectra

NASA Technical Reports Server (NTRS)

Stiller, G. P.; Gunson, M. R.; Lowes, L. L.; Abrams, M. C.; Raper, O. F.; Farmer, C. B.; Zander, R.; Rinsland, C. P.

1995-01-01

A simple, classical, and expedient method for the retrieval of atmospheric pressure-temperature profiles has been applied to the high-resolution infrared solar absorption spectra obtained with the atmospheric trace molecule spectroscopy (ATMOS) instrument. The basis for this method is a rotational analysis of retrieved apparent abundances from CO2 rovibrational absorption lines, employing existing constituent concentration retrieval software used in the analysis of data returned by ATMOS. Pressure-temperature profiles derived from spectra acquired during the ATLAS 1 space shuttle mission of March-April 1992 are quantitatively evaluated and compared with climatological and meteorological data as a means of assessing the validity of this approach.

Ab initio-informed maximum entropy modeling of rovibrational relaxation and state-specific dissociation with application to the O{sub 2} + O system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulakhmetov, Marat, E-mail: mkulakhm@purdue.edu; Alexeenko, Alina, E-mail: alexeenk@purdue.edu; Gallis, Michael, E-mail: magalli@sandia.gov

Quasi-classical trajectory (QCT) calculations are used to study state-specific ro-vibrational energy exchange and dissociation in the O{sub 2} + O system. Atom-diatom collisions with energy between 0.1 and 20 eV are calculated with a double many body expansion potential energy surface by Varandas and Pais [Mol. Phys. 65, 843 (1988)]. Inelastic collisions favor mono-quantum vibrational transitions at translational energies above 1.3 eV although multi-quantum transitions are also important. Post-collision vibrational favoring decreases first exponentially and then linearly as Δv increases. Vibrationally elastic collisions (Δv = 0) favor small ΔJ transitions while vibrationally inelastic collisions have equilibrium post-collision rotational distributions. Dissociationmore » exhibits both vibrational and rotational favoring. New vibrational-translational (VT), vibrational-rotational-translational (VRT) energy exchange, and dissociation models are developed based on QCT observations and maximum entropy considerations. Full set of parameters for state-to-state modeling of oxygen is presented. The VT energy exchange model describes 22 000 state-to-state vibrational cross sections using 11 parameters and reproduces vibrational relaxation rates within 30% in the 2500–20 000 K temperature range. The VRT model captures 80 × 10{sup 6} state-to-state ro-vibrational cross sections using 19 parameters and reproduces vibrational relaxation rates within 60% in the 5000–15 000 K temperature range. The developed dissociation model reproduces state-specific and equilibrium dissociation rates within 25% using just 48 parameters. The maximum entropy framework makes it feasible to upscale ab initio simulation to full nonequilibrium flow calculations.« less

Electron density diagnositc line ratios from the n = 3 lines of O v

DOE Office of Scientific and Technical Information (OSTI.GOV)

Widing, K.G.; Doyle, J.G.; Dufton, P.L.

New atomic physic calculations are presented for electron excitation rates for transitions between the n = 2 and n = 3 levels of O v. These are used to calculate theoretical line intensity ratios for the 192 A, 215 A, 220 A and 248 A lines of O v. These line intensity ratios are electron density sensitive and provide valuable diagnostics at T/sub e/approx.2 x 10/sup 5/ K for samll impulsive flare events in which the transition zone ions are enhanced relative to the coronal ions. Two flares observed by NRL spectroheliograph on Skylab, on 1973 December 22 and 1974more » January 21, are studied, with electron densities of approximately 3 x 10/sup 11/ cm/sup -3/ being deduced.« less

ExoMol line lists - XXII. The rotation-vibration spectrum of silane up to 1200 K

NASA Astrophysics Data System (ADS)

Owens, A.; Yachmenev, A.; Thiel, W.; Tennyson, J.; Yurchenko, S. N.

2017-11-01

A variationally computed 28SiH4 rotation-vibration line list applicable for temperatures up to T = 1200 K is presented. The line list, called OY2T, considers transitions with rotational excitation up to J = 42 in the wavenumber range 0-5000 cm-1 (wavelengths λ > 2 μm). Just under 62.7 billion transitions have been calculated between 6.1 million energy levels. Rovibrational calculations have utilized a new `spectroscopic' potential energy surface determined by empirical refinement to 1452 experimentally derived energy levels up to J = 6, and a previously reported ab initio dipole moment surface. The temperature-dependent partition function of silane, the OY2T line list format, and the temperature dependence of the OY2T line list are discussed. Comparisons with the PNNL spectral library and other experimental sources indicate that the OY2T line list is robust and able to accurately reproduce weaker intensity features. The full line list is available from the ExoMol data base and the CDS data base.

Water absorption lines, 931-961 nm - Selected intensities, N2-collision-broadening coefficients, self-broadening coefficients, and pressure shifts in air

NASA Technical Reports Server (NTRS)

Giver, L. P.; Gentry, B.; Schwemmer, G.; Wilkerson, T. D.

1982-01-01

Intensities were measured for 97 lines of H2O vapor between 932 and 961 nm. The lines were selected for their potential usefulness for remote laser measurements of H2O vapor in the earth's atmosphere. The spectra were obtained with several different H2O vapor abundances and N2 broadening gas pressures; the spectral resolution was 0.046/cm FWHM. Measured H2O line intensities range from 7 x 10 to the -25th to 7 x 10 to the -22nd/cm per (molecules/sq cm). H2O self-broadening coefficients were measured for 13 of these strongest lines; the mean value was 0.5/cm per atm. N2-collision-broadening coefficients were measured for 73 lines, and the average was 0.11 cm per atm HWHM. Pressure shifts in air were determined for a sample of six lines between 948 and 950 nm; these lines shift to lower frequency by an amount comparable to 0.1 of the collision-broadened widths measured in air or N2. The measured intensities of many lines of 300-000 band are much larger than expected from prior computations, in some cases by over an order of magnitude. Coriolis interactions with the stronger 201-000 band appear to be the primary cause of the enhancement of these line intensities.

Fluorescence Excitation Models of Ammonia and Amidogen Radical (NH2) in Comets: Application to Comet C/2004 Q2 (Machholz)

NASA Technical Reports Server (NTRS)

Kawakita, Hideyo; Mumma, Michael J.

2011-01-01

Ammonia is a major reservoir of nitrogen atoms in cometary materials. However, detections of ammonia in comets are rare, with several achieved at radio wavelengths. A few more detections were obtained through near-infrared observations (around the 3 m wavelength region), but moderate relative velocity shifts are required to separate emission lines of cometary ammonia from telluric absorption lines in the 3 micron wavelength region. On the other hand, the amidogen radical (NH2 -- a photodissociation product of ammonia in the coma) also shows rovibrational emission lines in the 3 micron wavelength region. Thus, gas production rates for ammonia can be determined from the rovibrational emission lines of ammonia (directly) and amidogen radical (indirectly) simultaneously in the near-infrared. In this article, we present new fluorescence excitation models for cometary ammonia and amidogen radical in the near-infrared, and we apply these models to the near-infrared high-dispersion spectra of comet C/2004 Q2 (Machholz) to determine the mixing ratio of ammonia to water in the comet. Based on direct detection of NH3 lines, the mixing ratio of NH3/H2O is 0.46% +/- 0.03% in C/2004 Q2 (Machholz), in agreement with other results. The mixing ratio of ammonia determined from the NH2 observations (0.31% -- 0.79%) is consistent but has relatively larger error, owing to uncertainty in the photodissociation rates of ammonia. At the present level of accuracy, we confirm that NH3 could be the sole parent of NH2 in this comet.

CO2 infrared emission as a diagnostic of planet-forming regions of disks

NASA Astrophysics Data System (ADS)

Bosman, Arthur D.; Bruderer, Simon; van Dishoeck, Ewine F.

2017-05-01

Context. The infrared ro-vibrational emission lines from organic molecules in the inner regions of protoplanetary disks are unique probes of the physical and chemical structure of planet-forming regions and the processes that shape them. These observed lines are mostly interpreted with local thermal equilibrium (LTE) slab models at a single temperature. Aims: We aim to study the non-LTE excitation effects of carbon dioxide (CO2) in a full disk model to evaluate: (I) what the emitting regions of the different CO2 ro-vibrational bands are; (II) how the CO2 abundance can be best traced using CO2 ro-vibrational lines using future JWST data and; (III) what the excitation and abundances tell us about the inner disk physics and chemistry. CO2 is a major ice component and its abundance can potentially test models with migrating icy pebbles across the iceline. Methods: A full non-LTE CO2 excitation model has been built starting from experimental and theoretical molecular data. The characteristics of the model are tested using non-LTE slab models. Subsequently the CO2 line formation was modelled using a two-dimensional disk model representative of T Tauri disks where CO2 is detected in the mid-infrared by the Spitzer Space Telescope. Results: The CO2 gas that emits in the 15 μm and 4.5 μm regions of the spectrum is not in LTE and arises in the upper layers of disks, pumped by infrared radiation. The v2 15 μm feature is dominated by optically thick emission for most of the models that fit the observations and increases linearly with source luminosity. Its narrowness compared with that of other molecules stems from a combination of the low rotational excitation temperature ( 250 K) and the inherently narrower feature for CO2. The inferred CO2 abundances derived for observed disks range from 3 × 10-9 to 1 × 10-7 with respect to total gas density for typical gas/dust ratios of 1000, similar to earlier LTE disk estimates. Line-to-continuum ratios are low, in the order of a

Spectral Line Parameters Including Temperature Dependences of Self- and Air-Broadening in the 2 (left arrow) 0 Band of CO at 2.3 micrometers

NASA Technical Reports Server (NTRS)

Devi, V. Malathy; Benner, D. Chris; Smith, M. A. H.; Mantz, A. W.; Sung, K.; Brown, L. R.; Predoi-Cross, A.

2012-01-01

Temperature dependences of pressure-broadened half-width and pressure-induced shift coefficients along with accurate positions and intensities have been determined for transitions in the 2<--0 band of C-12 O-16 from analyzing high-resolution and high signal-to-noise spectra recorded with two different Fourier transform spectrometers. A total of 28 spectra, 16 self-broadened and 12 air-broadened, recorded using high- purity (greater than or equal to 99.5% C-12-enriched) CO samples and CO diluted with dry air(research grade) at different temperatures and pressures, were analyzed simultaneously to maximize the accuracy of the retrieved parameters. The sample temperatures ranged from 150 to 298K and the total pressures varied between 5 and 700 Torr. A multispectrum nonlinear least squares spectrum fitting technique was used to adjust the rovibrational constants (G, B, D, etc.) and intensity parameters (including Herman-Wallis coefficients), rather than determining individual line positions and intensities. Self-and air-broadened Lorentz half-width coefficients, their temperature dependence exponents, self- and air-pressure-induced shift coefficients, their temperature dependences, self- and air-line mixing coefficients, their temperature dependences and speed dependence have been retrieved from the analysis. Speed-dependent line shapes with line mixing employing off-diagonal relaxation matrix element formalism were needed to minimize the fit residuals. This study presents a precise and complete set of spectral line parameters that consistently reproduce the spectrum of carbon monoxide over terrestrial atmospheric conditions.

Rovibrational optical pumping of a molecular beam

NASA Astrophysics Data System (ADS)

Cournol, A.; Pillet, P.; Lignier, H.; Comparat, D.

2018-03-01

The preparation of molecules in well-defined internal states is essential for various studies in fundamental physics and physical chemistry. It is thus of particular interest to find methods that increase the brightness of molecular beams. Here, we report on rotational and vibrational pumpings of a supersonic beam of barium monofluoride molecules. With respect to previous works, the time scale of optical vibrational pumping has been greatly reduced by enhancing the spectral power density in the vicinity of the appropriate molecular transitions. We demonstrate a complete transfer of the rovibrational populations lying in v″=1 -3 into the vibrational ground-state v″=0 . Rotational pumping, which requires efficient vibrational pumping, has been also demonstrated. According to a Maxwell-Boltzmann description, the rotational temperature of our sample has been reduced by a factor of ˜8 . In this fashion, the population of the lowest rotational levels increased by more than one order of magnitude.

Extension of the MIRS computer package for the modeling of molecular spectra: From effective to full ab initio ro-vibrational Hamiltonians in irreducible tensor form

NASA Astrophysics Data System (ADS)

Nikitin, A. V.; Rey, M.; Champion, J. P.; Tyuterev, Vl. G.

2012-07-01

The MIRS software for the modeling of ro-vibrational spectra of polyatomic molecules was considerably extended and improved. The original version [Nikitin AV, Champion JP, Tyuterev VlG. The MIRS computer package for modeling the rovibrational spectra of polyatomic molecules. J Quant Spectrosc Radiat Transf 2003;82:239-49.] was especially designed for separate or simultaneous treatments of complex band systems of polyatomic molecules. It was set up in the frame of effective polyad models by using algorithms based on advanced group theory algebra to take full account of symmetry properties. It has been successfully used for predictions and data fitting (positions and intensities) of numerous spectra of symmetric and spherical top molecules within the vibration extrapolation scheme. The new version offers more advanced possibilities for spectra calculations and modeling by getting rid of several previous limitations particularly for the size of polyads and the number of tensors involved. It allows dealing with overlapping polyads and includes more efficient and faster algorithms for the calculation of coefficients related to molecular symmetry properties (6C, 9C and 12C symbols for C3v, Td, and Oh point groups) and for better convergence of least-square-fit iterations as well. The new version is not limited to polyad effective models. It also allows direct predictions using full ab initio ro-vibrational normal mode Hamiltonians converted into the irreducible tensor form. Illustrative examples on CH3D, CH4, CH3Cl, CH3F and PH3 are reported reflecting the present status of data available. It is written in C++ for standard PC computer operating under Windows. The full package including on-line documentation and recent data are freely available at http://www.iao.ru/mirs/mirs.htm or http://xeon.univ-reims.fr/Mirs/ or http://icb.u-bourgogne.fr/OMR/SMA/SHTDS/MIRS.html and as supplementary data from the online version of the article.

14NH_3 Line Positions and Intensities in the Far-Infrared Comparison of Ft-Ir Measurements to Empirical Hamiltonian Model Predictions

NASA Astrophysics Data System (ADS)

Sung, Keeyoon; Yu, Shanshan; Pearson, John; Pirali, Olivier; Kwabia Tchana, F.; Manceron, Laurent

2016-06-01

We have analyzed multiple spectra of high purity (99.5%) normal ammonia sample recorded at room temperatures using the FT-IR and AILES beamline at Synchrotron SOLEIL, France. More than 2830 line positions and intensities are measured for the inversion-rotation and rovibrational transitions in the 50 - 660 wn region. Quantum assignments were made for 2047 transitions from eight bands including four inversion-rotation bands (gs(a-s), νb{2}(a-s), 2νb{2}(a-s), and νb{4}(a-s)) and four ro-vibrational bands (νb{2} - gs, 2νb{2} - gs, νb{4} - νb{2}, and 2νb{2} -νb{4}), as well as covering more than 300 lines of ΔK = 3 forbidden transitions. Out of the eight bands, we note that 2νb{2} - νb{4} has not been listed in the HITRAN 2012 database. The measured line positions for the assigned transitions are in an excellent agreement (typically better than 0.001 wn) with the predictions from the empirical Hamiltonian model [S. Yu, J.C. Pearson, B.J. Drouin, et al.(2010)] in a wide range of J and K for all the eight bands. The comparison with the HITRAN 2012 database is also satisfactory, although systematic offsets are seen for transitions with high J and K and those from weak bands. However, differences of 20% or so are seen in line intensities for allowed transitions between the measurements and the model predictions, depending on the bands. We have also noticed that most of the intensity outliers in the Hamiltonian model predictions belong to transitions from gs(a-s) band. We present the final results of the FT-IR measurements of line positions and intensities, and their comparisons to the model predictions and the HITRAN 2012 database. Research described in this paper was performed at the Jet Propulsion Laboratory and California Institute of Technology, under contracts and cooperative agreements with the National Aeronautics and Space Administration.

Line-Mixing Relaxation Matrix model for spectroscopic and radiative transfer studies

NASA Astrophysics Data System (ADS)

Mendaza, Teresa; Martin-Torres, Javier

2016-04-01

We present a generic model to compute the Relaxation Matrix easily adaptable to any molecule and type of spectroscopic lines or bands in non-reactive molecule collisions regimes. It also provides the dipole moment of every transition and level population of the selected molecule. The model is based on the Energy-Corrected Sudden (ECS) approximation/theory introduced by DePristo (1980), and on previous Relaxation Matrix studies for the interaction between molecular ro-vibrational levels (Ben-Rueven, 1966), atoms (Rosenkranz, 1975), linear molecules (Strow and Reuter, 1994; Niro, Boulet and Hartmann, 2004), and symmetric but not linear molecules (Tran et al., 2006). The model is open source, and it is user-friendly. To the point that the user only has to select the wished molecule and vibrational band to perform the calculations. It reads the needed spectroscopic data from the HIgh-resolution TRANsmission molecular absorption (HITRAN) (Rothman et al., 2013) and ExoMol (Tennyson and Yurchenko, 2012). In this work we present an example of the calculations with our model for the case of the 2ν3 band of methane (CH4), and a comparison with a previous work (Tran et al., 2010). The data produced by our model can be used to characterise the line-mixing effects on ro-vibrational lines of the infrared emitters of any atmosphere, to calculate accurate absorption spectra, that are needed in the interpretation of atmospheric spectra, radiative transfer modelling and General Circulation Models (GCM). References [1] A.E. DePristo, Collisional influence on vibration-rotation spectral line shapes: A scaling theoretical analysis and simplification, J. Chem. Phys. 73(5), 1980. [2] A. Ben-Reuven, Impact broadening of microwave spectra, Phys. Rev. 145(1), 7-22, 1966. [3] P.W. Rosenkranz, Shape of the 5 mm Oxygen Band in the Atmosphere, IEEE Transactions on Antennas and Propagation, vol. AP-23, no. 4, pp. 498-506, 1975. [4] Strow, L.L., D.D. Tobin, and S.E. Hannon, A compilation of

Loss of N-Cadherin Expression in Tumor Transplants Produced From As+3- and Cd+2-Transformed Human Urothelial (UROtsa) Cell Lines.

PubMed

Sandquist, Elizabeth J; Somji, Seema; Dunlevy, Jane R; Garrett, Scott H; Zhou, Xu Dong; Slusser-Nore, Andrea; Sens, Donald A

2016-01-01

Epithelial to mesenchymal transition is a process in which a cell experiences a loss of epithelial cell characteristics and acquires a more mesenchymal cell phenotype. In cancer, epithelial to mesenchymal transition has been proposed to play an important role during specific stages of tumor progression. The role epithelial to mesenchymal transition and mesenchymal to epithelial transition might play in toxicant-induced urothelial cancer is unknown. Real-time PCR, Western blotting, immuno-histochemistry and immuno-fluorescence were used to determine the expression of E- and N-cadherin in the UROtsa parent, the As+3- and Cd+2-transformed cell lines, the spheroids isolated from these cell lines as well as the tumor heterotransplants that were produced by the injection of the transformed cells into immune compromised mice. This study showed that N-cadherin expression was increased in 6 As+3- and 7 Cd+2- transformed cell lines generated from human urothelial cells (UROtsa). The expression varied within each cell line, with 10% to 95% of the cells expressing N-cadherin. Tumors produced from these cell lines showed no expression of the N-cadherin protein. Spheroids which are made up of putative cancer initiating cells produced from these cell lines showed only background expression of N-cadherin mRNA, increased expression of aldehyde dehydrogenase 1 mRNA and produced tumors which did not express N-cadherin. There was no change in the expression of E-cadherin in the tumors, and the tumors formed by all the As+3 and Cd+2-transformed cell lines and cancer initiating cells stained intensely and uniformly for E-cadherin. The finding that the cells expressing N-cadherin gave rise to tumors with no expression of N-cadherin is in agreement with the classical view of epithelial to mesenchymal transition. Epithelial to mesenchymal transition and N-cadherin are associated with dissemination and not with the ability to establish new tumor growth. Mesenchymal to epithelial transition

Insulin receptor in mouse neuroblastoma cell line N18TG2: binding properties and visualization with colloidal gold.

PubMed

Sartori, C; Stefanini, S; Bernardo, A; Augusti-Tocco, G

1992-08-01

Insulin function in the nervous system is still poorly understood. Possible roles as a neuromodulator and as a growth factor have been proposed (Baskin et al., 1987, Ann. Rev. Physiol. 49, 335-347). Stable cell lines may provide an appropriate experimental system for the analysis of insulin action on the various cellular components of the central nervous system. We report here a study to investigate the presence and the properties of insulin specific binding sites in the murine neuroblastoma line, N18TG2, together with insulin action on cell growth and metabolism. Also, receptor internalization has been studied. Binding experiments, carried out in standard conditions at 20 degrees C, enabled us to demonstrate that these cells bind insulin in a specific manner, thus confirming previous findings on other cell lines. Saturation curves showed the presence of two binding sites with Kd 0.3 and 9.7 nM. Competition experiments with porcine and bovine insulin showed an IC50 of 1 and 10 nM, respectively. Competition did not occur in the presence of the unrelated hormones ACTH and FSH. Dissociation experiments indicated the existence of an internalization process of the ligand-receptor complex; this was confirmed by an ultrastructural study using gold conjugated insulin. As far as the insulin action in N18TG2 cells is concerned, physiological concentrations stimulate cell proliferation, whereas no stimulation of glucose uptake was observed, indicating that insulin action in these cells is not mediated by general metabolic effects. On the basis of these data, N18TG2 line appears to be a very suitable model for further studies of the neuronal type insulin receptors, and possibly insulin specific action on the nervous system.

Theoretical Studies of N2-broadened Half-widths of H2O Lines Involving High j States

NASA Technical Reports Server (NTRS)

Ma, Q.; Tipping, R. H.; Lavrentieva, N. N.

2012-01-01

Based on the properties of the energy levels and wave functions of H2O states, one can categorize H2O lines into individually defined groups such that within the same group, the energy levels and the wave functions associated with two paired lines have an identity property while those associated with different pairs have a similarity property. Meanwhile, by thoroughly analyzing processes used to calculate N2-broadened half-widths, it was found that the 'Fourier series' of W(sup a)(sub L(sub 1))(sub K(sub 1))(sub K(sub 1)) (t; j(sub f) T(sub f) and W(sup a)(sub L(sub 1))(sub K(sub 1))(sub K(sub 1)) (t; j(sub i) T(sub i), and a factor P(sub 222) (j(sub f) T(sub f) j(sub i) T(sub i)) are the key items in the Robert-Bonamy formalism to distinguish contributions to ReS2(r(sub c)) among different transitions of j(sub f) T(sub f) - j(sub i). However, these items are completely determined by the energy levels and the wave functions associated with their initial and final states and they must bear the latter's features as well. Thus, it becomes obvious that for two paired lines in the same group, their calculated half-widths must be almost identical and the values associated with different pairs must vary smoothly as their ji values vary. Thus, the pair identity and the smooth variation rules are established within individual groups of lines. One can use these rules to screen half-width data listed in HITRAN and to improve the data accuracies.

Infrared spectra and tunneling dynamics of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O.

PubMed

Zhu, Yu; Zheng, Rui; Li, Song; Yang, Yu; Duan, Chuanxi

2013-12-07

The rovibrational spectra of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O have been measured in a supersonic slit jet expansion using a rapid-scan tunable diode laser spectrometer. Both a-type and b-type transitions were observed for these two complexes. All transitions are doubled, due to the heavy water tunneling within the complexes. Assuming the tunneling splittings are the same in K(a) = 0 and K(a) = 1, the band origins, all three rotational and several distortion constants of each tunneling state were determined for N2-D2O in the ground and excited vibrational states, and for OC-D2O in the excited vibrational state, respectively. The averaged band origin of OC-D2O is blueshifted by 2.241 cm(-1) from that of the v2 band of the D2O monomer, compared with 1.247 cm(-1) for N2-D2O. The tunneling splitting of N2-D2O in the ground state is 0.16359(28) cm(-1), which is about five times that of OC-D2O. The tunneling splittings decrease by about 26% for N2-D2O and 23% for OC-D2O, respectively, upon excitation of the D2O bending vibration, indicating an increase of the tunneling barrier in the excited vibrational state. The tunneling splittings are found to have a strong dependence on intramolecular vibrational excitation as well as a weak dependence on quantum number K(a).

Comparison of line-peak and line-scanning excitation in two-color laser-induced-fluorescence thermometry of OH.

PubMed

Kostka, Stanislav; Roy, Sukesh; Lakusta, Patrick J; Meyer, Terrence R; Renfro, Michael W; Gord, James R; Branam, Richard

2009-11-10

Two-line laser-induced-fluorescence (LIF) thermometry is commonly employed to generate instantaneous planar maps of temperature in unsteady flames. The use of line scanning to extract the ratio of integrated intensities is less common because it precludes instantaneous measurements. Recent advances in the energy output of high-speed, ultraviolet, optical parameter oscillators have made possible the rapid scanning of molecular rovibrational transitions and, hence, the potential to extract information on gas-phase temperatures. In the current study, two-line OH LIF thermometry is performed in a well-calibrated reacting flow for the purpose of comparing the relative accuracy of various line-pair selections from the literature and quantifying the differences between peak-intensity and spectrally integrated line ratios. Investigated are the effects of collisional quenching, laser absorption, and the integration width for partial scanning of closely spaced lines on the measured temperatures. Data from excitation scans are compared with theoretical line shapes, and experimentally derived temperatures are compared with numerical predictions that were previously validated using coherent anti-Stokes-Raman scattering. Ratios of four pairs of transitions in the A2Sigma+<--X2Pi (1,0) band of OH are collected in an atmospheric-pressure, near-adiabatic hydrogen-air flame over a wide range of equivalence ratios--from 0.4 to 1.4. It is observed that measured temperatures based on the ratio of Q1(14)/Q1(5) transition lines result in the best accuracy and that line scanning improves the measurement accuracy by as much as threefold at low-equivalence-ratio, low-temperature conditions. These results provide a comprehensive analysis of the procedures required to ensure accurate two-line LIF measurements in reacting flows over a wide range of conditions.

A relativistic coupled-cluster interaction potential and rovibrational constants for the xenon dimer

NASA Astrophysics Data System (ADS)

Jerabek, Paul; Smits, Odile; Pahl, Elke; Schwerdtfeger, Peter

2018-01-01

An accurate potential energy curve has been derived for the xenon dimer using state-of-the-art relativistic coupled-cluster theory up to quadruple excitations accounting for both basis set superposition and incompleteness errors. The data obtained is fitted to a computationally efficient extended Lennard-Jones potential form and to a modified Tang-Toennies potential function treating the short- and long-range part separately. The vibrational spectrum of Xe2 obtained from a numerical solution of the rovibrational Schrödinger equation and subsequently derived spectroscopic constants are in excellent agreement with experimental values. We further present solid-state calculations for xenon using a static many-body expansion up to fourth-order in the xenon interaction potential including dynamic effects within the Einstein approximation. Again we find very good agreement with the experimental (face-centred cubic) lattice constant and cohesive energy.

Loss of N-Cadherin Expression in Tumor Transplants Produced From As+3- and Cd+2-Transformed Human Urothelial (UROtsa) Cell Lines

PubMed Central

Sandquist, Elizabeth J.; Somji, Seema; Dunlevy, Jane R.; Garrett, Scott H.; Zhou, Xu Dong; Slusser-Nore, Andrea

2016-01-01

Background Epithelial to mesenchymal transition is a process in which a cell experiences a loss of epithelial cell characteristics and acquires a more mesenchymal cell phenotype. In cancer, epithelial to mesenchymal transition has been proposed to play an important role during specific stages of tumor progression. The role epithelial to mesenchymal transition and mesenchymal to epithelial transition might play in toxicant-induced urothelial cancer is unknown. Methods Real-time PCR, Western blotting, immuno-histochemistry and immuno-fluorescence were used to determine the expression of E- and N-cadherin in the UROtsa parent, the As+3- and Cd+2-transformed cell lines, the spheroids isolated from these cell lines as well as the tumor heterotransplants that were produced by the injection of the transformed cells into immune compromised mice. Results This study showed that N-cadherin expression was increased in 6 As+3- and 7 Cd+2- transformed cell lines generated from human urothelial cells (UROtsa). The expression varied within each cell line, with 10% to 95% of the cells expressing N-cadherin. Tumors produced from these cell lines showed no expression of the N-cadherin protein. Spheroids which are made up of putative cancer initiating cells produced from these cell lines showed only background expression of N-cadherin mRNA, increased expression of aldehyde dehydrogenase 1 mRNA and produced tumors which did not express N-cadherin. There was no change in the expression of E-cadherin in the tumors, and the tumors formed by all the As+3 and Cd+2-transformed cell lines and cancer initiating cells stained intensely and uniformly for E-cadherin. Conclusions The finding that the cells expressing N-cadherin gave rise to tumors with no expression of N-cadherin is in agreement with the classical view of epithelial to mesenchymal transition. Epithelial to mesenchymal transition and N-cadherin are associated with dissemination and not with the ability to establish new tumor growth

Air- and N2-Broadening Coefficients and Pressure-Shift Coefficients in the C-12(O2-16) Laser Bands

NASA Technical Reports Server (NTRS)

Devi, V. Malathy; Benner, D. Chris; Smith, Mary Ann H.; Rinsland, Curtis P.

1998-01-01

In this paper we report the pressure broadening and the pressure-induced line shift coefficients for 46 individual rovibrational lines in both the (12)C(16)O2, 00(sup 0)1-(10(sup 0)0-02(sup 0)0)I, and 00(sup 0)1-(10(sup 0)0-02(sup 0)0)II, laser bands (laser band I centered at 960.959/cm and laser band II centered at 1063.735/cm) determined from spectra recorded with the McMath-Pierce Fourier transform spectrometer. The results were obtained from analysis of 10 long-path laboratory absorption spectra recorded at room temperature using a multispectrum nonlinear least-squares technique. Pressure effects caused by both air and nitrogen have been investigated. The air-broadening coefficients determined in this study agree well with the values in the 1996 HITRAN database; ratios and standard deviations of the ratios of the present air-broadening measurements to the 1996 HITRAN values for the two laser bands are: 1.005(15) for laser band I and 1.005(14) for laser band II. Broadening by nitrogen is 3 to 4% larger than that of air. The pressure-induced line shift coefficients are found to be transition dependent and different for the P- and R-branch lines with same J" value. No noticeable differences in the shift coefficients caused by air and nitrogen were found. The results obtained are compared with available values previously reported in the literature.

Temperature Measurements in the Solar Transition Region Using N III Line Intensity Ratios

NASA Technical Reports Server (NTRS)

Doron, R.; Doschek, G. A.; Laming, J. M.; Feldman, U.; Bhatia, A. K.

2003-01-01

UV emission from B-like N and O ions a rather rare opportunity for recording spectral lines in a narrow wavelength range that can potentially be used to derive temperatures relevant to the solar transition region. In these ions, the line intensity ratios of the type (2s2p(sup 2) - 2p(sup 3)) / (2s(sup 2)2p - 2s2p(sup 2)) are very sensitive to the electron temperature. Additionally, the lines involving the ratios fall within a range of only - 12 A; in N III the lines fall in the 980 - 992 A range and in O IV in the 780 - 791 A range. In this work, we explore the use of these atomic systems, primarily in N III, for temperature diagnostics of the transition region by analyzing UV spectra obtained by the Solar Ultraviolet Measurements of Emitted Radiation (SUMER) spectrometer flown on the Solar and Heliospheric Observatory (SOHO). The N III temperature-sensitive line ratios are measured in more than 60 observations. Most of the measured ratios correspond to temperatures in the range 5.7x10(exp 4) - 6.7x10(exp 4) K. This range is considerably lower than the calculated temperature of maximum abundance of N III, which is approx. 7.6x10(exp 4) K. Detailed analysis of the spectra further indicates that the measured ratios are probably somewhat overestimated due to resonant scattering effects in the 2s(sup 2)2p - 2s2p(sup 2) lines and small blends in the 2s2p(sup 2) - 2p3 lines. Actual lower ratios would only increase the disagreement between the ionization balance calculations and present temperature measurements based on a collisional excitation model. In the case of the O IV spectra, we determined that due to the close proximity in wavelength of the weak line (2s2p(sup 2)-2p3 transitions) to a strong Ne VIII line, sufficiently accurate ratio measurements cannot be obtained. Subject headings: atomic data --- atomic processes --- Sun: transition region --- Sun: U V radiation --- techniques: spectroscopic

Complex organic molecules in the interstellar medium: IRAM 30 m line survey of Sagittarius B2(N) and (M)

NASA Astrophysics Data System (ADS)

Belloche, A.; Müller, H. S. P.; Menten, K. M.; Schilke, P.; Comito, C.

2013-11-01

Context. The discovery of amino acids in meteorites fallen to Earth and the detection of glycine, the simplest of them, in samples returned from a comet to Earth strongly suggest that the chemistry of the interstellar medium is capable of producing such complex organic molecules and that they may be widespread in our Galaxy. Aims: Our goal is to investigate the degree of chemical complexity that can be reached in the interstellar medium, in particular in dense star-forming regions. Methods: We performed an unbiased, spectral line survey toward Sgr B2(N) and (M), two regions where high-mass stars are formed, with the IRAM 30 m telescope in the 3 mm atmospheric transmission window. Partial surveys at 2 and 1.3 mm were performed in parallel. The spectra were analyzed with a simple radiative transfer model that assumes local thermodynamic equilibrium but takes optical depth effects into account. Results: About 3675 and 945 spectral lines with a peak signal-to-noise ratio higher than 4 are detected at 3 mm toward Sgr B2(N) and (M), i.e. about 102 and 26 lines per GHz, respectively. This represents an increase by about a factor of two over previous surveys of Sgr B2. About 70% and 47% of the lines detected toward Sgr B2(N) and (M) are identified and assigned to 56 and 46 distinct molecules as well as to 66 and 54 less abundant isotopologues of these molecules, respectively. In addition, we report the detection of transitions from 59 and 24 catalog entries corresponding to vibrationally or torsionally excited states of some of these molecules, respectively, up to a vibration energy of 1400 cm-1 (2000 K). Excitation temperatures and column densities were derived for each species but should be used with caution. The rotation temperatures of the detected complex molecules typically range from ~50 to 200 K. Among the detected molecules, aminoacetonitrile, n-propyl cyanide, and ethyl formate were reported for the first time in space based on this survey, as were five rare

Rovibrational spectra of ammonia. I. Unprecedented accuracy of a potential energy surface used with nonadiabatic corrections.

PubMed

Huang, Xinchuan; Schwenke, David W; Lee, Timothy J

2011-01-28

In this work, we build upon our previous work on the theoretical spectroscopy of ammonia, NH(3). Compared to our 2008 study, we include more physics in our rovibrational calculations and more experimental data in the refinement procedure, and these enable us to produce a potential energy surface (PES) of unprecedented accuracy. We call this the HSL-2 PES. The additional physics we include is a second-order correction for the breakdown of the Born-Oppenheimer approximation, and we find it to be critical for improved results. By including experimental data for higher rotational levels in the refinement procedure, we were able to greatly reduce our systematic errors for the rotational dependence of our predictions. These additions together lead to a significantly improved total angular momentum (J) dependence in our computed rovibrational energies. The root-mean-square error between our predictions using the HSL-2 PES and the reliable energy levels from the HITRAN database for J = 0-6 and J = 7∕8 for (14)NH(3) is only 0.015 cm(-1) and 0.020∕0.023 cm(-1), respectively. The root-mean-square errors for the characteristic inversion splittings are approximately 1∕3 smaller than those for energy levels. The root-mean-square error for the 6002 J = 0-8 transition energies is 0.020 cm(-1). Overall, for J = 0-8, the spectroscopic data computed with HSL-2 is roughly an order of magnitude more accurate relative to our previous best ammonia PES (denoted HSL-1). These impressive numbers are eclipsed only by the root-mean-square error between our predictions for purely rotational transition energies of (15)NH(3) and the highly accurate Cologne database (CDMS): 0.00034 cm(-1) (10 MHz), in other words, 2 orders of magnitude smaller. In addition, we identify a deficiency in the (15)NH(3) energy levels determined from a model of the experimental data.

N III Bowen Lines and Fluorescence Mechanism in the Symbiotic Star AG Peg

NASA Astrophysics Data System (ADS)

Hyung, Siek; Lee, Seong-Jae; Lee, Kang Hwan

2018-03-01

We have investigated the intensities and full width at half maximum (FWHM) of the high dispersion spectroscopic N III emission lines of AG Peg, observed with the Hamilton Echelle Spectrograph (HES) in three different epochs at Mt. Hamilton's Lick Observatory. The earlier theoretical Bowen line study assumed the continuum fluorescence effect, presenting a large discrepancy with the present data. Hence, we analyzed the observed N III lines assuming line fluorescence as the only suitable source: (1) The O III and N III resonance line profiles near λ 374 were decomposed, using the Gaussian function, and the contributions from various O III line components were determined. (2) Based on the theoretical resonant N III intensities, the expected N III Bowen intensities were obtained to fit the observed values. Our study shows that the incoming line photon number ratio must be considered to balance at each N III Bowen line level in the ultraviolet radiation according to the observed lines in the optical zone. We also found that the average FWHM of the N III Bowen lines was about 5 km·s-1 greater than that of the O III Bowen lines, perhaps due to the inherently different kinematic characteristics of their emission zones.

Communication: Visible line intensities of the triatomic hydrogen ion from experiment and theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrignani, Annemieke; Berg, Max H.; Grussie, Florian

2014-12-28

The visible spectrum of H{sub 3}{sup +} is studied using high-sensitivity action spectroscopy in a cryogenic radiofrequency multipole trap. Advances are made to measure the weak ro-vibrational transitions from the lowest rotational states of H{sub 3}{sup +} up to high excitation energies providing visible line intensities and, after normalisation to an infrared calibration line, the corresponding Einstein B coefficients. Ab initio predictions for the Einstein B coefficients are obtained from a highly precise dipole moment surface of H{sub 3}{sup +} and found to be in excellent agreement, even in the region where states have been classified as chaotic.

The NaK 1 1,3delta states: theoretical and experimental studies of fine and hyperfine structure of rovibrational levels near the dissociation limit.

PubMed

Wilkins, A D; Morgus, L; Hernandez-Guzman, J; Huennekens, J; Hickman, A P

2005-09-22

Earlier high-resolution spectroscopic studies of the fine and hyperfine structure of rovibrational levels of the 1 3delta state of NaK have been extended to include high lying rovibrational levels with v < or = 59, of which the highest levels lie within approximately 4 cm(-1) of the dissociation limit. A potential curve is determined using the inverted perturbation approximation method that reproduces these levels to an accuracy of approximately 0.026 cm(-1). For the largest values of v, the outer turning points occur near R approximately 12.7 angstroms, which is sufficiently large to permit the estimation of the C6 coefficient for this state. The fine and hyperfine structure of the 1 3delta rovibrational levels has been fit using the matrix diagonalization method that has been applied to other states of NaK, leading to values of the spin-orbit coupling constant A(v) and the Fermi contact constant b(F). New values determined for v < or = 33 are consistent with values determined by a simpler method and reported earlier. The measured fine and hyperfine structure for v in the range 44 < or = v < or = 49 exhibits anomalous behavior whose origin is believed to be the mixing between the 1 3delta and 1 1delta states. The matrix diagonalization method has been extended to treat this interaction, and the results provide an accurate representation of the complicated patterns that arise. The analysis leads to accurate values for A(v) and b(F) for all values of v < or = 49. For higher v (50 < or = v < or = 59), several rovibrational levels have been assigned, but the pattern of fine and hyperfine structure is difficult to interpret. Some of the observed features may arise from effects not included in the current model.

Infrared spectra of seeded hydrogen clusters: (para-H2)N-N2O and (ortho-H2)N-N2O, N = 2-13.

PubMed

Tang, Jian; McKellar, A R W

2005-09-15

High-resolution infrared spectra of clusters containing para-H2 and/or ortho-H2 and a single nitrous oxide molecule are studied in the 2225-cm(-1) region of the upsilon1 fundamental band of N2O. The clusters are formed in pulsed supersonic jet expansions from a cooled nozzle and probed using a tunable infrared diode laser spectrometer. The simple symmetric rotor-type spectra generally show no resolved K structure, with prominent Q-branch features for ortho-H2 but not para-H2 clusters. The observed vibrational shifts and rotational constants are reported. There is no obvious indication of superfluid effects for para-H2 clusters up to N=13. Sharp transitions due to even larger clusters are observed, but no definite assignments are possible. Mixed (para-H2)N-(ortho-H2)M-N2O cluster line positions can be well predicted by linear interpolation between the corresponding transitions of the pure clusters.

Ro-vibrational Spectra of (para-H2 )N -CH4 in He Droplets.

PubMed

Hoshina, Hiromichi; Sliter, Russell; Ravi, Aakash; Kuma, Susumu; Momose, Takamasa; Vilesov, Andrey F

2016-11-18

In this work, we report on the infrared spectroscopic study of clusters of CH 4 molecules with up to N=80 para-hydrogen molecules assembled inside He droplets. Upon increase of the number of the added para-hydrogen molecules up to about N=12, both the rotational constant, B, and the origin frequency of the υ 3 band of CH 4 decrease gradually. In the range of 6 ≤N≤12, the spectra indicate some abrupt changes of B and υ 3 with both values being approximately constant at N≥12. The origin of this effect is discussed. Comparison of the spectra of methane molecules in para-hydrogen clusters to that in solid para-hydrogen is also presented. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Haze on Molecular Lines Formed in the Atmosphere of Titan

NASA Astrophysics Data System (ADS)

Kim, Sang J.

2012-10-01

Radiative transfer calculations for the ro-vibrational lines of CH4, C2H2, C2H6, and HCN in atmosphere of Titan have been carried out without consideration of haze opacities (e.g., Yelle and Griffith, 2003), or only for very high (z > 500 km) atmospheric layers where haze influence is assumed to be negligible (e.g., Adriani et al. 2011; and García-Comas et al. 2011). Haze particles are found to exist in the high-altitude atmosphere of Titan, where the absorption lines of these molecules are modified by the haze opacities (Bellucci et al. 2009; Kim et al. 2011). We will present a discussion on the influence of the haze opacities on these molecular lines based on a preliminary result from updated radiative transfer calculations. References Adriani, A. et al. 2011. Icarus 214, 584-595. Bellucci, A. et al. 2009. Icarus 201, 198-216. García-Comas, M. et al. 2011. Icarus 214, 571-583. Kim, et al. 2011. 2011. Planetary and Space Science 59, 699-704. Yelle, R.V., Griffith, C.A., 2003. Icarus 166, 107-115.

CO AND H{sub 2} ABSORPTION IN THE AA TAURI CIRCUMSTELLAR DISK

DOE Office of Scientific and Technical Information (OSTI.GOV)

France, Kevin; Burgh, Eric B.; Schindhelm, Eric

2012-01-01

The direct study of molecular gas in inner protoplanetary disks is complicated by uncertainties in the spatial distribution of the gas, the time variability of the source, and the comparison of observations across a wide range of wavelengths. Some of these challenges can be mitigated with far-ultraviolet spectroscopy. Using new observations obtained with the Hubble Space Telescope Cosmic Origins Spectrograph, we measure column densities and rovibrational temperatures for CO and H{sub 2} observed on the line of sight through the AA Tauri circumstellar disk. CO A - X absorption bands are observed against the far-UV continuum. The CO absorption ismore » characterized by log{sub 10}(N({sup 12}CO)) = 17.5 {+-} 0.5 cm{sup -2} and T{sub rot}(CO) = 500{sup +500}{sub -200} K, although this rotational temperature may underestimate the local kinetic temperature of the CO-bearing gas. We also detect {sup 13}CO in absorption with an isotopic ratio of {approx}20. We do not observe H{sub 2} absorption against the continuum; however, hot H{sub 2} (v > 0) is detected in absorption against the Ly{alpha} emission line. We measure the column densities in eight individual rovibrational states, determining a total log{sub 10}(N(H{sub 2})) = 17.9{sup +0.6}{sub -0.3} cm{sup -2} with a thermal temperature of T(H{sub 2}) = 2500{sup +800}{sub -700} K. The high temperature of the molecules, the relatively small H{sub 2} column density, and the high inclination of the AA Tauri disk suggest that the absorbing gas resides in an inner disk atmosphere. If the H{sub 2} and CO are cospatial within a molecular layer {approx}0.6 AU thick, this region is characterized by {approx} 10{sup 5} cm{sup -3} with an observed (CO/H{sub 2}) ratio of {approx}0.4. We also find evidence for a departure from a purely thermal H{sub 2} distribution, suggesting that excitation by continuum photons and H{sub 2} formation may be altering the level populations in the molecular gas.« less

Gas Phase Molecular Spectroscopy: Electronic Spectroscopy of Combustion Intermediates, Chlorine Azide kinetics, and Rovibrational Energy Transfer in Acetylene

NASA Astrophysics Data System (ADS)

Freel, Keith A.

This dissertation is composed of three sections. The first deals with the electronic spectroscopy of combustion intermediates that are related to the formation of polycyclic aromatic hydrocarbons. Absorption spectra for phenyl, phenoxy, benzyl, and phenyl peroxy radicals were recorded using the technique of cavity ring-down spectroscopy. When possible, molecular constants, vibrational frequencies, and excited state lifetimes for these radicals were derived from these data. The results were supported by theoretical predictions. The second section presents a study of electron attachment to chlorine azide (ClN3) using a flowing-afterglow Langmuir-probe apparatus. Electron attachment rates were measured to be 3.5x10-8 and 4.5x10-8 cm3s-1 at 298 and 400 K respectively. The reactions of ClN3 with eighteen cations and seventeen anions were characterized. Rate constants were measured using a selected ion flow tube. The ionization energy (>9.6eV), proton affinity (713+/-41 kJ mol-1), and electron affinity (2.48+/-0.2 eV) for ClN 3 were determined from these data. The third section demonstrates the use of double resonance spectroscopy to observe state-selected rovibrational energy transfer from the first overtone asymmetric stretch of acetylene. The total population removal rate constants from various rotational levels of the (1,0,1,00,00) vibrational state were determined to be in the range of (9-17) x 10 -10 cm3s-1. Rotational energy transfer accounted for approximately 90% of the total removal rate from each state. Therefore, the upper limit of vibrational energy transfer from the (1,0,1,0 0,00) state was 10%.

Accurate Quantum Wave Packet Study of the Deep Well D+ + HD Reaction: Product Ro-vibrational State-Resolved Integral and Differential Cross Sections.

PubMed

He, Haixiang; Zhu, Weimin; Su, Wenli; Dong, Lihui; Li, Bin

2018-03-08

The H + + H 2 reaction and its isotopic variants as the simplest triatomic ion-molecule reactive system have been attracting much interests, however there are few studies on the titled reaction at state-to-state level until recent years. In this work, accurate state-to-state quantum dynamics studies of the titled reaction have been carried out by a reactant Jacobi coordinate-based time-dependent wave packet approach on diabatic potential energy surfaces constructed by Kamisaka et al. Product ro-vibrational state-resolved information has been calculated for collision energies up to 0.2 eV with maximal total angular momentum J = 40. The necessity of including all K-component for accounting the Coriolis coupling for the reaction has been illuminated. Competitions between the two product channels, (D + + HD' → D' + + HD and D + + HD' → H + + DD') were investigated. Total integral cross sections suggest that resonances enhance the reactivity of channel D + + HD'→ H + + DD', however, resonances depress the reactivity of the another channel D + + HD' → D' + + HD. The structures of the differential cross sections are complicated and depend strongly on collision energies of the two channels and also on the product rotational states. All of the product ro-vibrational state-resolved differential cross sections for this reaction do not exhibit rigorous backward-forward symmetry which may indicate that the lifetimes of the intermediate resonance complexes should not be that long. The dynamical observables of this deuterated isotopic reaction are quite different from the reaction of H + + H 2 → H 2 + H + reported previously.

Using monomer vibrational wavefunctions to compute numerically exact (12D) rovibrational levels of water dimer

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2018-02-01

We compute numerically exact rovibrational levels of water dimer, with 12 vibrational coordinates, on the accurate CCpol-8sf ab initio flexible monomer potential energy surface [C. Leforestier et al., J. Chem. Phys. 137, 014305 (2012)]. It does not have a sum-of-products or multimode form and therefore quadrature in some form must be used. To do the calculation, it is necessary to use an efficient basis set and to develop computational tools, for evaluating the matrix-vector products required to calculate the spectrum, that obviate the need to store the potential on a 12D quadrature grid. The basis functions we use are products of monomer vibrational wavefunctions and standard rigid-monomer basis functions (which involve products of three Wigner functions). Potential matrix-vector products are evaluated using the F matrix idea previously used to compute rovibrational levels of 5-atom and 6-atom molecules. When the coupling between inter- and intra-monomer coordinates is weak, this crude adiabatic type basis is efficient (only a few monomer vibrational wavefunctions are necessary), although the calculation of matrix elements is straightforward. It is much easier to use than an adiabatic basis. The product structure of the basis is compatible with the product structure of the kinetic energy operator and this facilitates computation of matrix-vector products. Compared with the results obtained using a [6 + 6]D adiabatic approach, we find good agreement for the inter-molecular levels and larger differences for the intra-molecular water bend levels.

Using monomer vibrational wavefunctions to compute numerically exact (12D) rovibrational levels of water dimer.

PubMed

Wang, Xiao-Gang; Carrington, Tucker

2018-02-21

We compute numerically exact rovibrational levels of water dimer, with 12 vibrational coordinates, on the accurate CCpol-8sf ab initio flexible monomer potential energy surface [C. Leforestier et al., J. Chem. Phys. 137, 014305 (2012)]. It does not have a sum-of-products or multimode form and therefore quadrature in some form must be used. To do the calculation, it is necessary to use an efficient basis set and to develop computational tools, for evaluating the matrix-vector products required to calculate the spectrum, that obviate the need to store the potential on a 12D quadrature grid. The basis functions we use are products of monomer vibrational wavefunctions and standard rigid-monomer basis functions (which involve products of three Wigner functions). Potential matrix-vector products are evaluated using the F matrix idea previously used to compute rovibrational levels of 5-atom and 6-atom molecules. When the coupling between inter- and intra-monomer coordinates is weak, this crude adiabatic type basis is efficient (only a few monomer vibrational wavefunctions are necessary), although the calculation of matrix elements is straightforward. It is much easier to use than an adiabatic basis. The product structure of the basis is compatible with the product structure of the kinetic energy operator and this facilitates computation of matrix-vector products. Compared with the results obtained using a [6 + 6]D adiabatic approach, we find good agreement for the inter-molecular levels and larger differences for the intra-molecular water bend levels.

N2O molecular tagging velocimetry

NASA Astrophysics Data System (ADS)

ElBaz, A. M.; Pitz, R. W.

2012-03-01

A new seeded velocity measurement technique, N2O molecular tagging velocimetry (MTV), is developed to measure velocity in wind tunnels by photochemically creating an NO tag line. Nitrous oxide "laughing gas" is seeded into the air flow. A 193 nm ArF excimer laser dissociates the N2O to O(1D) that subsequently reacts with N2O to form NO. O2 fluorescence induced by the ArF laser "writes" the original position of the NO line. After a time delay, the shifted NO line is "read" by a 226-nm laser sheet and the velocity is determined by time-of-flight. At standard atmospheric conditions with 4% N2O in air, ˜1000 ppm of NO is photochemically created in an air jet based on experiment and simulation. Chemical kinetic simulations predict 800-1200 ppm of NO for 190-750 K at 1 atm and 850-1000 ppm of NO for 0.25-1 atm at 190 K. Decreasing the gas pressure (or increasing the temperature) increases the NO ppm level. The presence of humid air has no significant effect on NO formation. The very short NO formation time (<10 ns) makes the N2O MTV method amenable to low- and high-speed air flow measurements. The N2O MTV technique is demonstrated in air jet to measure its velocity profile. The N2O MTV method should work in other gas flows as well (e.g., helium) since the NO tag line is created by chemical reaction of N2O with O(1D) from N2O photodissociation and thus does not depend on the bulk gas composition.

Rovibrational states of Wigner molecules in spherically symmetric confining potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cioslowski, Jerzy

2016-08-07

The strong-localization limit of three-dimensional Wigner molecules, in which repulsively interacting particles are confined by a weak spherically symmetric potential, is investigated. An explicit prescription for computation of rovibrational wavefunctions and energies that are asymptotically exact at this limit is presented. The prescription is valid for systems with arbitrary angularly-independent interparticle and confining potentials, including those involving Coulombic and screened (i.e., Yukawa/Debye) interactions. The necessary derivations are greatly simplified by explicit constructions of the Eckart frame and the parity-adapted primitive wavefunctions. The performance of the new formalism is illustrated with the three- and four-electron harmonium atoms at their strong-correlation limits.more » In particular, the involvement of vibrational modes with the E symmetry is readily pinpointed as the origin of the “anomalous” weak-confinement behavior of the {sup 1}S{sub +} state of the four-electron species that is absent in its {sup 1}D{sub +} companion of the strong-confinement regime.« less

Comparison of Trajectory Models in Calculations of N2-broadened Half-widths and N2-induced Line Shifts for the Rotational Band of H2O-16 and Comparison with Measurements

NASA Technical Reports Server (NTRS)

Lamouroux, J.; Gamache, R. R.; Laraia, A. L.; Ma, Q.; Tipping, R. H.

2012-01-01

In this work, Complex Robert-Bonamy calculations of half-widths and line shifts were done for N2-broadening of water for 1639 transitions in the rotational band using two models for the trajectories. The first is a model correct to second order in time, the Robert-Bonamy parabolic approximation. The second is the solution of Hamilton's equations. Both models use the isotropic part of the atom-atom potential to determine the trajectories. The present calculations used an intermolecular potential expanded to 20th order to assure the convergence of the half-widths and line shifts. The aim of the study is to assess if the difference in the half-widths and line shifts determined from the two trajectory models is greater than the accuracy requirements of the spectroscopic and remote sensing communities. The results of the calculations are compared with measurements of the half-widths and line shifts. It is shown that the effects of the trajectory model greatly exceed the needs of current remote sensing measurements and that line shape parameters calculated using trajectories determined by solving Hamilton's equations agree better with measurement.

Vibrational and rotational excitation effects of the N(2D) + D2(X1Σg +) → ND(X3Σ+) + D(2S) reaction

NASA Astrophysics Data System (ADS)

Zhu, Ziliang; Wang, Haijie; Wang, Xiquan; Shi, Yanying

2018-05-01

The effects of the rovibrational excitation of reactants in the N(2D) + D2(X1Σg+) → ND(X3Σ+) + D(2S) reaction are calculated in a collision energy range from the threshold to 1.0 eV using the time-dependent wave packet approach and a second-order split operator. The reaction probability, integral cross-section, differential cross-section and rate constant of the title reaction are calculated. The integral cross-section and rate constant of the initial states v = 0, j = 0, 1, are in good agreement with experimental data available in the literature. The rotational excitation of the D2 molecule has little effect on reaction probability, integral cross-section and the rate constant, but it increased the sideways and forward scattering signals. The vibrational excitation of the D2 molecule reduced the threshold and broke up the forward-backward symmetry of the differential cross-section; it also increased the forward scattering signals. This may be because the vibrational excitation of the D2 molecule reduced the lifetime of the intermediate complex.

Influence of velocity effects on the shape of N2 (and air) broadened H2O lines revisited with classical molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Ngo, N. H.; Tran, H.; Gamache, R. R.; Bermejo, D.; Domenech, J.-L.

2012-08-01

The modeling of the shape of H2O lines perturbed by N2 (and air) using the Keilson-Storer (KS) kernel for collision-induced velocity changes is revisited with classical molecular dynamics simulations (CMDS). The latter have been performed for a large number of molecules starting from intermolecular-potential surfaces. Contrary to the assumption made in a previous study [H. Tran, D. Bermejo, J.-L. Domenech, P. Joubert, R. R. Gamache, and J.-M. Hartmann, J. Quant. Spectrosc. Radiat. Transf. 108, 126 (2007)], 10.1016/j.jqsrt.2007.03.009, the results of these CMDS show that the velocity-orientation and -modulus changes statistically occur at the same time scale. This validates the use of a single memory parameter in the Keilson-Storer kernel to describe both the velocity-orientation and -modulus changes. The CMDS results also show that velocity- and rotational state-changing collisions are statistically partially correlated. A partially correlated speed-dependent Keilson-Storer model has thus been used to describe the line-shape. For this, the velocity changes KS kernel parameters have been directly determined from CMDS, while the speed-dependent broadening and shifting coefficients have been calculated with a semi-classical approach. Comparisons between calculated spectra and measurements of several lines of H2O broadened by N2 (and air) in the ν3 and 2ν1 + ν2 + ν3 bands for a wide range of pressure show very satisfactory agreement. The evolution of non-Voigt effects from Doppler to collisional regimes is also presented and discussed.

Resolving shocked and UV excited components of H2 emission in planetary nebulae with high-resolution near-infrared spectroscopy

NASA Astrophysics Data System (ADS)

Kaplan, Kyle; Dinerstein, Harriet L.; Jaffe, Daniel Thomas

2016-06-01

Planetary nebulae (PNe) form when low and intermediate-mass stars eject their outer layers into the ISM at the end of the AGB phase. Many PNe exhibit near-infrared (NIR) emission from molecular hydrogen (H2). This NIR emission arises from radiative decay out of excited rotation-vibration (rovibrational) states. The rovibrational states can be populated by excitation to higher electronic states through absorption of a far-UV photon followed by a radiative cascade to the electronic ground state, or by collisions (e.g., in a hot gas). The two processes populate the rovibrational levels of H2 differently, so the observed emergent emission spectrum provides an effective probe of the mechanisms that excite the H2. Many PNe display line intensity ratios that are intermediate between these two processes (Otsuka et al. 2013). With the advantages of the high spectral resolution (R~40000), broad wavelength coverage (1.45-2.45 μm), and high spatial resolution of the Immersion GRating Infrared Spectrometer (IGRINS, Park et al. 2014), we are able to differentiate components in position-velocity space: we see a slowly expanding UV-excited H2 shell in the PN M 1-11 and two faster moving “bullets” of thermalized H2 that we interpret as shocked gas from a bipolar outflow. We also present observations of several other PNe that exhibit similar morphologies of thermalized and UV-excited H2 components.

VizieR Online Data Catalog: Sgr B2(N) and Sgr B2(M) IRAM 30m line survey (Belloche+, 2013)

NASA Astrophysics Data System (ADS)

Belloche, A.; Mueller, H. S. P.; Menten, K. M.; Schilke, P.; Comito, C.

2013-08-01

The list of line identifications corresponding to the blue labels in Figs. 2 to 7 where the labels are often too crowded to be easily readable are available in ASCII format. The lists are split into six files, three for Sgr B2(N) and three for Sgr B2(M). For each source, there is one file per atmospheric window (3, 2, and 1mm). Each file is ordered by increasing frequency. The observed and synthetic spectra of Sgr B2(N) and Sgr B2(M) between 80 and 116GHz are available both in ASCII and FITS formats. The synthetic spectra were resampled to the same frequency channels as the observed spectra. The blanking value is -1000K for the ASCII files. There is one ASCII file per source. There are two FITS files per source, one for the observed spectrum and one for the synthetic spectrum. The intensities are in main-beam temperature scale in K. The blanking value is 42.75234K for the observed spectrum of SgrB2(N) and 53.96533K for the observed spectrum of SgrB2(M). (9 data files).

Dynamic processes in Be star atmospheres. 2: He I 2P-nD line formation in lambda Eridani (outburst)

NASA Technical Reports Server (NTRS)

Smith, Myron A.; Hubeny, Ivan; Lanz, Thierry; Meylan, Thomas

1994-01-01

The He I lambda 6678 line of early Be stars generally shows violet (V) and red (R) emission whenever hydrogen alpha emission is present, but its use as a diagnostic has been handicapped by a poor understanding of the processes that drive it into emission. In an attempt to address this problem we obtained three series of eschelle spectra of the first two members of the singlet and triplet 2P-nD series of lambda Eri (B2e) during 1992 November 3-5 at Kitt Peak. During these observations lambda 6678 showed substantial emission variability in both the wings and central profile, providing an opportunity to compare its behavior with that of the lambda 4922, lambda 5876, and lambda 4471 lines. We found that the responses of the lines were different in several respects. Whereas the emissions in the V wings of all four lines scaled together, the R wing of the lambda 4922 line invariably responded with increased absorption whenever the R wing of lambda 6678 line showed increased emission. These same trends occurred within the central photospheric profiles. The R-wing behavior shows that much, but not all of the emission in lambda 6678 is caused by matter projected against the stellar disk. The excitation temperatures of the neighboring 2(sup 1) P transitions, lambda 6678 and lambda 4922 must be greater than and less than the photospheric continuum temperature, respectively. We have investigated departures from local thermodynamic equilibrium (LTE) for the He I spectrum in a variety of ad hoc, perturbed model atmospheres. We have found only one way to cause the source function of lambda 6678 to increase so strongly, namely, by increasing the atmospheric temperature in the line formation region to 30,000 - 40,000 K. This effect was discovered by Auer and Mihalas for O3-O4 atmospheric models, but it has not been applied to active B stars. Our models suggest that lambda 6678 emission in Be stars can be used as a sensitive monitor of localized hot spots on these stars' surfaces

Search for the OH (X(2)Pi) Meinel band emission in meteors as a tracer of mineral water in comets: detection of N(2)(+) (A-X)

NASA Technical Reports Server (NTRS)

Jenniskens, Peter; Laux, Christophe O.

2004-01-01

We report the discovery of the N(2)(+) A-X Meinel band in the 780-840 nm meteor emission from two Leonid meteoroids that were ejected less than 1000 years ago by comet 55P/Tempel-Tuttle. Our analysis indicates that the N(2)(+) molecule is at least an order of magnitude less abundant than expected, possibly as a result of charge transfer reactions with meteoric metal atoms. This new band was found while searching for rovibrational transitions in the X(2)Pi electronic ground state of OH (the OH Meinel band), a potential tracer of water bound to minerals in cometary matter. The electronic A-X transition of OH has been identified in other Leonid meteors. We did not detect this OH Meinel band, which implies that the excited A state is not populated by thermal excitation but by a mechanism that directly produces OH in low vibrational levels of the excited A(2)Sigma state. Ultraviolet dissociation of atmospheric or meteoric water vapor is such a mechanism, as is the possible combustion of meteoric organics.

Polarizability tensor invariants of H2, HD, and D2

NASA Astrophysics Data System (ADS)

Raj, Ankit; Hamaguchi, Hiro-o.; Witek, Henryk A.

2018-03-01

We report an exhaustive compilation of wavelength-dependent matrix elements over the mean polarizability (α ¯ ) and polarizability anisotropy (γ) operators for the rovibrational states of the H2, HD, and D2 molecules together with an accompanying computer program for their evaluation. The matrix elements can be readily evaluated using the provided codes for rovibrational states with J = 0-15 and v = 0-4 and for any laser wavelengths in the interval 182.25-1320.6 nm corresponding to popular, commercially available lasers. The presented results substantially extend the scope of the data available in the literature, both in respect of the rovibrational transitions analyzed and the range of covered laser frequencies. The presented detailed tabulation of accurate polarizability tensor invariants is essential for successful realization of our main long-term goal: developing a universal standard for determining absolute Raman cross sections and absolute Raman intensities in experimental Rayleigh and Raman scattering studies of molecules.

Oxygen vibrations in the series Bi2Sr2Ca{_{n-1}}Cu{n}O{_{4+2 n+y}}

NASA Astrophysics Data System (ADS)

Faulques, E.; Dupouy, P.; Lefrant, S.

1991-06-01

We present a discussion of the oxygen vibrations in the Bi{2}Sr{2}Ca{n-1}Cu{n}O{4+2 n+y} high T_c superconductors with the aim of interpreting Raman spectra in the case of the non-symmorphic Amaa structure. Group theory shows that the oxygen atoms belonging to the central CuO{2} plane generate a Raman activity for the n=1,3 phases. Consequently, we propose a novel assignment for the lines of weak intensity at 297, 316 and 333 cm^{-1}. It is shown that the two components of the 460 cm^{-1} band may be consistent with the Amma structure. Spectra recorded in crossed polarization exhibit weak lines which could be assigned to B {1g} modes expected for the three phases. Nous présentons une discussion sur les vibrations des atomes d'oxygène dans la série des supraconducteurs Bi{2}Sr{2}Ca{n-1}Cu{n}O{4+2 n+y} dans le but d'interpréter les spectres Raman. L'analyse des modes normaux de vibration de la structure Amaa pour les phases n=1 ou 3 montre que les atomes d'oxygène du plan CuO{2} contenant les centres d'inversion donnent lieu à une activité Raman. En conséquence, nous proposons une nouvelle attribution pour les raies de faible intensité à 297, 316 et 333 cm^{-1}. Nous montrons que le dédoublement de la bande à 460 cm^{-1} pourrait être dû à la structure Amaa. Les spectres enregistrés en polarization croisée montrent de faibles bandes qui peuvent être attribuées aux modes B {1g} attendus pour les trois phases.

First Detections of the [N II] 122 micron Line at High Redshift: Demonstrating the Utility of the Line for Studying Galaxies in the Early Universe

NASA Technical Reports Server (NTRS)

Ferkinhoff, Carl; Brisbin, Drew; Nikola, Thomas; Parshley, Stephen C.; Stacey, Gordon J.; Phillips, Thomas G.; Falgarone, Edith; Benford, Dominic J.; Staguhn, Johannes G.; Tucker, Carol E.

2011-01-01

We report the first detections of the [N II] 122 micron line from a high-redshift galaxy. The line was strongly (>6(sigma)) detected from SMMJ02399-0136, and H1413 + 117 (the Cloverleaf QSO) using the Redshift (zeta) and Early Universe Spectrometer on the Caltech Submillimeter Observatory. The lines from both sources are quite bright with line to far-infrared (FIR) continuum luminosity ratios that are approx.7.0 x 10(exp -4) (Cloverleaf) and 2.1 x 10(exo -3) (SMMJ02399). With ratios 2-10 times larger than the average value for nearby galaxies, neither source exhibits the line to continuum deficits seen in nearby sources. The line strengths also indicate large ionized gas fractions, approx.8%-17% of the molecUlar gas mass. The [O III]/[N II] line ratio is very sensitive to the effective temperature of ionizing stars and the ionization parameter for emission arising in the narrow-line region (NLR) of an active galactic nucleus (AGN). Using Our previous detection of the [O III] 88 micron line, the [O III]/[N II]line ratio for SMMJ02399-0136 indicates that the dominant source of the line emission is either stellar H II regions ionized by O9.5 stars, or the NLR of the AGN with ionization parameter log(U) = -3.3 to -4.0. A composite system, where 30%-50% of the FIR lines arise in the NLR also matches the data. The Cloverleaf is best modeled by a superposition of approx.200 M82-like starbursts accounting for all of the FIR emission and 43% of the [N II]line. The remainder may come from the NLR. This war!< demonstrates the utility of the [N II] and [O III] lines in constraining properties of the ionized medium.

Probing the Gaseous Disk of T Tau N with CN 5-4 Lines

NASA Technical Reports Server (NTRS)

Podio, L.; Kamp, I.; Codella, C.; Nisini, B.; Aresu, G.; Brittain, S.; Cabrit, S.; Dougados, C.; Grady, C.; Meijerink, R.;

DIRECT DETERMINATION OF THE HF/H{sub 2} ABUNDANCE RATIO IN INTERSTELLAR GAS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Indriolo, Nick; Neufeld, D. A.; Seifahrt, A.

2013-02-20

We report the first detection of the v = 1-0, R(0) ro-vibrational transition of HF at 2.499385 {mu}m arising from interstellar gas. The line is seen in absorption toward three background sources-HD 154368, Elias 29, and AFGL 2136 IRS 1-all of which have reported H{sub 2} column densities determined from observations of H{sub 2}. This allows for the first direct determination of the HF/H{sub 2} abundance ratio. We find values of N(HF)/N(H{sub 2}) = 1.15 Multiplication-Sign 10{sup -8} and 0.69 Multiplication-Sign 10{sup -8} for HD 154368 and Elias 29, respectively. The sight line toward AFGL 2136 IRS 1 also showsmore » absorption from the v = 1-0, R(1) transition of HF, indicating warm, dense (n {sub H} {approx}> 10{sup 9} cm{sup -3}) gas, likely very close to the central protostar. Ascribing portions of the HF absorption to warm and cold gas, we find N(HF)/N(H{sub 2}) = (1.7-2.9) Multiplication-Sign 10{sup -8} and (0.33-0.58) Multiplication-Sign 10{sup -8} for the two components, respectively. Except for the warm component toward AFGL 2136 IRS 1, all observed HF/H{sub 2} ratios are well below N(HF)/N(H{sub 2}) = 3.6 Multiplication-Sign 10{sup -8}, the value predicted if nearly all gas phase fluorine is in the form of HF. Models of fluorine chemistry that account for depletion onto grains are able to reproduce the results toward HD 154368, but not in the cold, dense gas toward AFGL 2136 IRS 1 and Elias 29. Most likely, some combinations of simplifying assumptions made in the chemical models are responsible for these discrepancies.« less

Observations of D/H ratios in H2O, HCl, and HF on Venus and new DCl and DF line strengths

NASA Astrophysics Data System (ADS)

Krasnopolsky, V. A.; Belyaev, D. A.; Gordon, I. E.; Li, G.; Rothman, L. S.

2013-05-01

Intensities of the spectral lines in the fundamental bands of D35Cl and DF were calculated using the semi-empirical dipole moment functions derived from the most accurate and precise measurements of intensities of the ro-vibrational lines of H35Cl and HF. Values obtained in this way for the deuterated species are superior to any available measured or calculated data to date. Our study of the D/H ratios in H2O, HCl, and HF on Venus is based on spatially-resolved high-resolution spectroscopy using the CSHELL spectrograph at NASA IRTF. Search for DF on Venus using its R5 (1-0) line at 3024.054 cm-1 results in a DF mixing ratio of 0.23 ± 0.11 ppb that corresponds to (D/H)HF = 420 ± 200 times that in the Standard Mean Ocean Water (SMOW). H2O abundances on Venus were retrieved using lines at 3022.366 and 3025.761 cm-1 that were observed at an exceptionally low overhead telluric water abundance of 0.3 pr. mm. The measured H2O mixing ratios at 74 km vary insignificantly between 55°S and 55°N with a mean value of 3.2 ppm. When compared with simultaneous observations of HDO near 2722 cm-1, this results in (D/H)H2O = 95 ± 15 times SMOW. Reanalysis of the observation of the D35Cl R4 (1-0) line at 2141.540 cm-1 (Krasnopolsky, V.A. [2012b]. Icarus 219, 244-249) using the improved line strength and more thorough averaging of the spectra gives (D/H)HCl = 190 ± 50 times SMOW. The similarity of the measured (D/H)H2O = 95 ± 15 at 74 km with 120 ± 40 observed by De Bergh et al. (De Bergh, C., Bezard, B., Owen, T., Crisp, D., Maillard, J.P., Lutz, B.L. [1991]. Science 251, 547-549) below the clouds favors the constant (D/H)H2O from the surface to the mesosphere, in accord with the prediction by theory. D/H ≈ 100 removes a difference of a factor of 2 between H2O abundances in the observations by Krasnopolsky (Krasnopolsky, V.A. [2010b]. Icarus 209, 314-322) and the Venus Express nadir observations (Cottini, V., Ignatiev, N.I., Piccioni, G., Drossart, P., Grassi, D., Markiewicz

Cytocompatibility of amorphous hydrogenated carbon nitride films deposited by CH4/N2 dielectric barrier discharge plasmas with respect to cell lines

NASA Astrophysics Data System (ADS)

Majumdar, Abhijit; Schröder, Karsten; Hippler, Rainer

2008-10-01

Special amorphous hydrogenated carbon nitride (a-H-CNx) films have been prepared on glass substrates for the investigation of adhesion and proliferation of different mammalian cell lines. CH4/N2 dielectric barrier discharge plasmas were applied to deposit a-H-CNx coatings at half of the atmospheric pressure. Film quality was modified by varying the CH4:N2 ratio and deposition duration. Chemical composition was determined by x-ray photoelectron spectroscopy and Fourier transformed infrared spectroscopy. The N/C ratio was in the range of 0.20-0.55. A very small surface roughness was verified by atomic force microscopy. Human embryonic kidney (HEK) and rat adrenal pheochromocytoma (PC12) cells were cultivated on the a-H-CNx films to investigate the cytocompatibility of these surfaces. The microscopic images show that both kinds of cells lines were unable to survive. The cells did not adhere to the surfaces, and most of the cells died after certain time spans. Increased amounts of nitrogen in the film induce an accelerated cell death. It is concluded, that the deposited CNx film behaves cytotoxic to HEK and PC12 cell lines.

SOFIA/EXES High Spectral Resolution Observations of the Orion Hot Core

NASA Astrophysics Data System (ADS)

Rangwala, Naseem; Colgan, Sean; Le Gal, Romane; Acharya, Kinsuk; Huang, Xinchuan; Herbst, Eric; Lee, Timothy J.; Richter, Matthew J.; Boogert, Adwin

2018-01-01

The Orion hot core has one of the richest molecular chemistries observed in the ISM. In the MIR, the Orion hot core composition is best probed by the closest, compact, bright background continuum source in this region, IRc2. We present high-spectral resolution observations from 12.96 - 13.33 μm towards Orion IRc2 using the mid-infrared spectrograph, EXES, on SOFIA, to probe the physical and chemical conditions of the Orion hot core. All ten of the rovibrational C2H2 transitions expected in our spectral coverage, are detected with high S/N, yielding continuous coverage of the R-branch lines from J=9-8 to J=18-17, including both ortho and para species. Eight of these rovibrational transitions are newly reported detections. These data show distinct ortho and para ladders towards the Orion hot core for the first time, with an ortho to para ratio (OPR) of only 0.6 - much lower than the high temperature equilibrium value of 3. A non-equilibrium OPR is a further indication of the Orion hot core being heated externally by shocks likely resulting from a well-known explosive event which occurred 500 yrs ago. The OPR conversion timescales are much longer than the 500 yr shock timescale and thus a low OPR might be a remnant from an earlier colder pre-stellar phase before the density enhancement (now the hot core) was impacted by shocks.We will also present preliminary results from an on-going SOFIA Cycle-5 impact program to use EXES to conduct an unbiased, high-S/N, continuous, molecular line survey of the Orion hot core from 12.5 - 28.3 microns. This survey is expected to be 50 times better than ISO in detecting isolated, narrow lines to (a) resolve the ro-vibrational structure of the gas phase molecules and their kinematics, (b) detect new gas phase molecules missed by ISO, and (c) provide useful constraints on the hot core chemistry and the source of Orion hot core excitation. This survey will greatly enhance the inventory of resolved line features in the MIR for hot cores

Communication: Saturated CO2 absorption near 1.6 μm for kilohertz-accuracy transition frequencies

NASA Astrophysics Data System (ADS)

Burkart, Johannes; Sala, Tommaso; Romanini, Daniele; Marangoni, Marco; Campargue, Alain; Kassi, Samir

2015-05-01

Doppler-free saturated-absorption Lamb dips were measured on weak rovibrational lines of 12C16O2 between 6189 and 6215 cm-1 at sub-Pa pressures using optical feedback frequency stabilized cavity ring-down spectroscopy. By referencing the laser source to an optical frequency comb, transition frequencies for ten lines of the 30013←00001 band P-branch and two lines of the 31113←01101 hot band R-branch were determined with an accuracy of a few parts in 1011. Involving rotational quantum numbers up to 42, the data were used for improving the upper level spectroscopic constants. These results provide a highly accurate reference frequency grid over the spectral interval from 1599 to 1616 nm.

Anharmonic Rovibrational Calculations of Singlet Cyclic C4 Using a New Ab Initio Potential and a Quartic Force

NASA Technical Reports Server (NTRS)

Wang, Xiaohong; Huang, Xinchuan; Bowman, Joel M.; Lee, Timothy J.

2013-01-01

We report a CCSD(T)/cc-pCV5Z quartic force field (QFF) and a semi-global CCSD(T)-F12b/aug-cc-pVTZ potential energy surface (PES) for singlet, cyclic C4. Vibrational fundamentals, combinations and overtones are obtained using vibrational second-order perturbation theory (VPT2) and the vibrational configurationinteraction (VCI) approach. Agreement is within 10 cm(exp -1) between the VCI calculated fundamentals on the QFF and PES using the MULTIMODE (MM) program, and VPT2 and VCI results agree for the fundamentals. The agreement between VPT2- QFF and MM-QFF results is also good for the C4 combinations and overtones. The J = 1 and J = 2 rovibrational energies are reported from both VCI (MM) on the PES and VPT2 on the QFF calculations. The spectroscopic constants of (12)C4 and two C(sub 2v)-symmetry, single (13)C-substituted isotopologues are presented, which may help identification of cyclic C4 in future experimental analyses or astronomical observations.

Naturally occurring glucagon-like peptide-2 (GLP-2) receptors in human intestinal cell lines.

PubMed

Sams, Anette; Hastrup, Sven; Andersen, Marie; Thim, Lars

2006-02-17

Although clinical trials with GLP-2 receptor agonists are currently ongoing, the mechanisms behind GLP-2-induced intestinal epithelial growth remain to be understood. To approach the GLP-2 mechanism of action this study aimed to identify intestinal cell lines endogenously expressing the GLP-2 receptor. Here we report the first identification of a cell line endogenously expressing functional GLP-2 receptors. The human intestinal epithelial cell line, FHC, expressed GLP-2 receptor encoding mRNA (RT-PCR) and GLP-2 receptor protein (Western blot). In cultured FHC cells, GLP-2 induced concentration dependent cAMP accumulation (pEC(50)=9.7+/-0.04 (mean+/-S.E.M., n=4)). In addition, a naturally occurring human intestinal fibroblast cell line, 18Co, endogenously expressing GLP-2 receptor encoding mRNA (RT-PCR) and protein (Western blot) was identified. No receptor functionality (binding or G-protein signalling) could be demonstrated in 18Co cells. The identified gut-relevant cell lines provide tools for future clarification of the mechanisms underlying GLP-2-induced epithelial growth.

Electron beam-generated Ar/N{sub 2} plasmas: The effect of nitrogen addition on the brightest argon emission lines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lock, E. H., E-mail: evgeniya.lock@nrl.navy.mil, E-mail: scott.walton@nrl.navy.mil; Petrova, Tz. B.; Petrov, G. M.

2016-04-15

The effect of nitrogen addition on the emission intensities of the brightest argon lines produced in a low pressure argon/nitrogen electron beam-generated plasmas is characterized using optical emission spectroscopy. In particular, a decrease in the intensities of the 811.5 nm and 763.5 nm lines is observed, while the intensity of the 750.4 nm line remains unchanged as nitrogen is added. To explain this phenomenon, a non-equilibrium collisional-radiative model is developed and used to compute the population of argon excited states and line intensities as a function of gas composition. The results show that the addition of nitrogen to argon modifies the electron energymore » distribution function, reduces the electron temperature, and depopulates Ar metastables in exchange reactions with electrons and N{sub 2} molecules, all of which lead to changes in argon excited states population and thus the emission originating from the Ar 4p levels.« less

Zinc affects miR-548n, SMAD4, SMAD5 expression in HepG2 hepatocyte and HEp-2 lung cell lines.

PubMed

Grider, Arthur; Lewis, Richard D; Laing, Emma M; Bakre, Abhijeet A; Tripp, Ralph A

2015-12-01

MicroRNAs affect disease progression and nutrient status. miR-548n increased 57 % in Zn supplemented plasma from adolescent females (ages 9 to 13 years). The purpose of this study was to determine the effects of Zn concentration in cell culture on the expression of miR-548n, SMAD4 and SMAD5 in hepatocyte (HepG2) and lung epithelium (HEp-2) cell lines. Cells were incubated for 48 h in media containing 10 % Chelex 100-treated FBS (0 μM Zn), or with 15 or 50 μM Zn, before isolation of total RNA and cDNA. Expression of miR-548n, SMAD4 and SMAD5 was measured by qPCR. The ΔΔCT method was used to calculate the fold-change, and 15 µM expression levels were used as reference values. HepG2 miR-548n expression decreased 5-fold, and SMAD4 expression increased 4-fold in the absence of Zn, while HEp-2 miR-548n expression increased 10.5-fold, and SMAD5 expression increased 20-fold in the absence of Zn. HEp-2 miR-548n expression increased 23-fold, while SMAD4 expression decreased twofold, in 50 μM Zn-treated cells. However, SMAD4 and SMAD5 expression was not correlated. These data indicate that miR-548n expression is in part regulated by Zn in a cell-specific manner. SMAD4 and SMAD5 are genes in the TGF-β/BMP signaling pathway, and SMAD5 is a putative target for miR-548n; Zn participates in regulating this pathway through controlling SMAD4 and SMAD5 expression. However, SMAD5 expression may be more sensitive to Zn than to miR-548n since SMAD5 expression was not inversely correlated with miR-548n expression.

First analysis of the rotationally-resolved ν 2 and 2ν 2-ν 2 bands of sulfur dioxide, 33S 16O 2

DOE PAGES

Blake, T. A.; Flaud, J. -M.; Lafferty, W. J.

2017-01-03

A Fourier transform spectrum of sulfur dioxide 33S 16O 2 has been recorded in the 18.3 μm spectral region at a resolution of 0.002 cm $-$1 using a Bruker IFS 125HR spectrometer leading to the observation of the ν 2 and 2ν 2-ν 2 vibrational bands of the 33S 16O 2 molecule. The corresponding upper state ro-vibrational levels were fit using Watson-type Hamiltonians. In this way it was possible to reproduce the upper state ro-vibrational levels to within the experimental uncertainty; i.e., ~ 0.20 × 10 $-$3 cm $-$1. Finally, very accurate rotational and centrifugal distortion constants were derived frommore » the fit together with the following band centers: ν 0 (ν 2) = 515.659089(50) cm $-$1, ν 0 (2ν 2) = 1030.697723(20) cm $-$1.« less

18 CFR 2.2 - Transmission lines.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 18 Conservation of Power and Water Resources 1 2011-04-01 2011-04-01 false Transmission lines. 2.2 Section 2.2 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF... Under the Federal Power Act § 2.2 Transmission lines. In a public statement dated March 7, 1941, the...

Methane Line Intensities: Near and Far IR

NASA Astrophysics Data System (ADS)

Brown, Linda R.; Devi, V. Malathy; Wishnow, Edward H.; Sung, Keeyoon; Crawford, Timothy J.; Mantz, Arlan W.; Smith, Mary Ann H.; Predoi-Cross, Adriana; Benner, D. Chris

2014-11-01

Accurate knowledge of line intensities is crucial input for radiance calculations to interpret atmospheric observations of planets and moons. We have therefore undertaken extensive laboratory studies to measure the methane spectrum line-by-line in order to improve theoretical quantum mechanical modeling for molecular spectroscopy databases (e. g. HITRAN and GEISA) used by planetary astronomers. Preliminary results will be presented for selected ro-vibrational transitions in both the near-IR (1.66 and 2.2 - 2.4 microns) and the far-IR (80 - 120 microns) regions. For this, we have recorded high-resolution spectra (instrumental resolving power: 1,300,000 (NIR) and 10,000 (FIR)) with the Bruker 125HR Fourier transform spectrometer at JPL using isotopically-enriched 12CH4 and 13CH4, as well as normal methane samples. For the NIR wavelengths, three different absorption cells have been employed to achieve sample temperatures ranging from 78 K to 299 K: 1) a White cell set to a path length of 13.09 m for room temperature data, 2) a single-pass 0.2038 m cold cell and 3) a new coolable Herriott cell with a fixed 20.941 m optical path and configured for the first time to a FT-IR spectrometer. For the Far-IR, another coolable absorption chamber set to a 52 m optical path has been used. These new experiments and intensity measurements will be presented and discussed.Part of the research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology, the University of California, Berkeley, Connecticut College, and NASA Langley under contracts and grants with the National Aeronautics and Space Administration. A. Predoi-Cross and her research group have been supported by the National Science and Engineering Research Council of Canada.

Fifteen terawatt picosecond CO2 laser system.

PubMed

Haberberger, D; Tochitsky, S; Joshi, C

2010-08-16

The generation of a record peak-power of 15 TW (45 J, 3 ps) in a single CO(2) laser beam is reported. Using a master oscillator-power amplifier laser system, it is shown that up to 100 J of energy can be extracted in a train of 3 ps laser pulses separated by 18 ps, a characteristic time of the CO(2) molecule. The bandwidth required for amplifying the short injected laser pulse train in a 2.5 atm final CO(2) amplifier is provided by field broadening of the medium at intensities of up to 140 GW/cm(2). The measured saturation energy for 3 ps pulses is 120 mJ/cm(2) which confirms that energy is simultaneously extracted from six rovibrational lines.

Simulating electric field interactions with polar molecules using spectroscopic databases

NASA Astrophysics Data System (ADS)

Owens, Alec; Zak, Emil J.; Chubb, Katy L.; Yurchenko, Sergei N.; Tennyson, Jonathan; Yachmenev, Andrey

2017-03-01

Ro-vibrational Stark-associated phenomena of small polyatomic molecules are modelled using extensive spectroscopic data generated as part of the ExoMol project. The external field Hamiltonian is built from the computed ro-vibrational line list of the molecule in question. The Hamiltonian we propose is general and suitable for any polar molecule in the presence of an electric field. By exploiting precomputed data, the often prohibitively expensive computations associated with high accuracy simulations of molecule-field interactions are avoided. Applications to strong terahertz field-induced ro-vibrational dynamics of PH3 and NH3, and spontaneous emission data for optoelectrical Sisyphus cooling of H2CO and CH3Cl are discussed.

Critical evaluation of measured line positions of 14N16O in X2П state

NASA Astrophysics Data System (ADS)

Sulakshina, O. N.; Borkov, Yu. G.

2018-04-01

All available line positions for unresolved and resolved Λ-doublets of the 14N16O molecule in the X2 П state were collected from the literature and tested using the RITZ computer code. These data have been critically analysed and used to obtain the most complete set of 1789 experimental energy levels of unresolved Λ-doublets covering the 0-35,866 cm-1 interval. A set of 425 experimental energy levels of resolved Λ-doublets covering the 0-5957 cm-1 interval for two states 2П1/2 and 2П3/2 also have been obtained. These levels together with calculated correlation matrix can be used to generate the precise list of transitions with confidence intervals. Comparisons with the HITRAN as well as with Amiot calculations are discussed. The systematic shift between experimental energy levels of unresolved Λ-doublets and those calculated by Amiot for 2П3/2 state was found. The same systematic shift for transitions frequencies of unresolved Λ-doublets in forbidden subbands 2П1/2↔2П3/2 is also established in the HITRAN database. Comparison of the RITZ energy levels with calculated energy levels by Wong at al. was also done. It was found, that experimental RITZ energy levels for resolved Λ-doublets of 14N16O coincide with those calculated by Wong at al. within experimental uncertainties.

Selective Adsorption Resonances in the Scattering of n-H2 p-H2 n-D2 and o-D2 from Ag(111)

NASA Astrophysics Data System (ADS)

Yu, Chien-Fan; Whaley, K. Birgitta; Hogg, Charles S.; Sibener, Steven J.

1983-12-01

Diffractive and rotationally mediated selective adsorption scattering resonances are reported for n-H2 p-H2 n-D2 and o-D2 on Ag(111). Small resonance shifts and line-width differences are observed between n-H2 and p-H2 indicating a weak orientation dependence of the laterally averaged H2/Ag(111) potential. The p-H2 and o-D2 levels were used to determine the isotropic component of this potential, yielding a well depth of ~ 32 meV.

Molecular dynamic simulations of N2-broadened methane line shapes and comparison with experiments

NASA Astrophysics Data System (ADS)

Le, Tuong; Doménech, José-Luis; Lepère, Muriel; Tran, Ha

2017-03-01

Absorption spectra of methane transitions broadened by nitrogen have been calculated for the first time using classical molecular dynamic simulations. For that, the time evolution of the auto-correlation function of the dipole moment vector, assumed along a C-H axis, was computed using an accurate site-site intermolecular potential for CH4-N2. Quaternion coordinates were used to treat the rotation of the molecules. A requantization procedure was applied to the classical rotation and spectra were then derived as the Fourier-Laplace transform of the auto-correlation function. These computed spectra were compared with experimental ones recorded with a tunable diode laser and a difference-frequency laser spectrometer. Specifically, nine isolated methane lines broadened by nitrogen, belonging to various vibrational bands and having rotational quantum numbers J from 0 to 9, were measured at room temperature and at several pressures from 20 to 945 mbar. Comparisons between measured and calculated spectra were made through their fits using the Voigt profile. The results show that ab initio calculated spectra reproduce with very high fidelity non-Voigt effects on the measurements and that classical molecular dynamic simulations can be used to predict spectral shapes of isolated lines of methane perturbed by nitrogen.

Electron Stark Broadening Database for Atomic N, O, and C Lines

NASA Technical Reports Server (NTRS)

Liu, Yen; Yao, Winifred M.; Wray, Alan A.; Carbon, Duane F.

2012-01-01

A database for efficiently computing the electron Stark broadening line widths for atomic N, O, and C lines is constructed. The line width is expressed in terms of the electron number density and electronatom scattering cross sections based on the Baranger impact theory. The state-to-state cross sections are computed using the semiclassical approximation, in which the atom is treated quantum mechanically whereas the motion of the free electron follows a classical trajectory. These state-to-state cross sections are calculated based on newly compiled line lists. Each atomic line list consists of a careful merger of NIST, Vanderbilt, and TOPbase line datasets from wavelength 50 nm to 50 micrometers covering the VUV to IR spectral regions. There are over 10,000 lines in each atomic line list. The widths for each line are computed at 13 electron temperatures between 1,000 K 50,000 K. A linear least squares method using a four-term fractional power series is then employed to obtain an analytical fit for each line-width variation as a function of the electron temperature. The maximum L2 error of the analytic fits for all lines in our line lists is about 5%.

VizieR Online Data Catalog: CH4 and hot methane continuum hybrid line list (Yurchenko+, 2017)

NASA Astrophysics Data System (ADS)

Yurchenko, S. N.; Amundsen, D. S.; Tennyson, J.; Waldmann, I. P.

2017-07-01

The states file ch4_e50.dat contains a list of rovibrational states. Each state is labelled with: nine normal mode vibrational quantum numbers and the vibrational symmetry; three rotational quantum numbers including the total angular momentum J and rotational symmetry; the total symmetry quantum number Gamma and the running number in the same (J,Gamma) block. In addition there are nine local mode vibrational numbers and the largest coefficient used to assign the state in question. Each rovibrational state has a unique number, which is the number of the row in which it appears in the file. This number is the means by which the state is related to the second part of the data system, the transitions files. The total degeneracy is also given to facilitate the intensity calculations. Because of their size, the transitions are listed in 120 separate files, each containing all the transitions in a 100cm-1 frequency range. These transition files t_*.dat contain the strong methane lines lines consisting of three columns: the reference number in the energy file of the upper state, that of the lower state, the Einstein A coefficient of the transition and the transition wavenumber. These entries are ordered by increasing frequency. The name of the file includes the lowest frequency in the range; thus the t-00500.dat file contains all the transitions in the frequency range 500-600cm-1. 19 histograms xYYYYK.dat files contain CH4_ super-lines representing the continuum computed at the temperature T=YYYYK using R=1000000 (7090081 super-lines each) covering the wavenumber range from 10 to 12000cm-1. The energy file, the transitions files and the histograms files are bzipped, and need to be extracted before use. The pressure broadening parameters used in the calculations are listed in broad.dat. A programme ExoCross to generate synthetic spectra from these line lists can be obtained at www.exomol.com. (4 data files).

Line Parameters of Carbon Dioxide in the 4850 CM-1 Region

NASA Astrophysics Data System (ADS)

Benner, D. Chris; Devi, V. Malathy; Nugent, Emily; Sung, Keeyoon; Brown, Linda R.; Miller, Charles E.; Toth, Robert A.

2011-06-01

The spectral region near 4850 Cm-1 is used to monitor atmospheric carbon dioxide, but current accuracies of the line intensities and line shape coefficients do not permit carbon dioxide mixing ratios to be obtained to 1 ppm (about one part in 400). To improve the line parameters, we are remeasuring the prominent CO2 bands in this region specifically to characterize the non-Voigt effects of line mixing and speed dependence at room temperature. The laboratory spectra of air- and self-broadened CO2 have been recorded at a variety of pressures, path lengths, mixing ratios and resolutions (0.005 to 0.01 Cm-1) with two different Fourier transform spectrometers (the McMath-Pierce FTS at Kitt Peak and a Bruker 125 HR FTS at JPL). The line parameters of some 2000 transitions are being derived by simultaneous multispectrum fitting using a few dozen spectra encompassing a 230 Cm-1 wide spectral interval. The rovibrational constants for line positions and the band intensities and Herman-Wallis coefficients are being retrieved directly from the spectra, rather than floating positions and intensities individually. Self and foreign Lorentz widths and pressure shifts are being determined for the stronger bands while non-Voigt coefficients describing line mixing and speed dependence are being obtained for at least one of the strongest bands. D. Chris Benner, C. P. Rinsland, V. M. Devi, M. A. H. Smith, and D. A. Atkins, JQSRT 1995;53:705-21. V. M. Devi, D. Chris Benner, L. R. Brown, C. E. Miller, and R. A. Toth, J. Mol. Spectrosc. 2007;245:52-80. Part of the research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contracts and cooperative agreements with the National Aeronautics and Space Administration. Support for the work at William and Mary was provided by contracts with JPL.

Ultrafast Two-Dimensional Infrared Spectroscopy of a Quasifree Rotor: J Scrambling and Perfectly Anticorrelated Cross Peaks

NASA Astrophysics Data System (ADS)

Mandal, Aritra; Ng Pack, Greg; Shah, Parth P.; Erramilli, Shyamsunder; Ziegler, L. D.

2018-03-01

Ultrafast two-dimensional infrared (2DIR) spectra of the N2O ν3 mode in moderately dense SF6 gas exhibit complex line shapes with diagonal and antidiagonal features in contrast to condensed phase vibrational 2DIR spectroscopy. Observed spectra for this quasifree rotor system are well captured by a model that includes all 36 possible rovibrational pathways and treats P (Δ J =-1 ) and R (Δ J =+1 ) branch resonances as distinct Kubo line shape features. Transition frequency correlation decay is due to J scrambling within one to two gas collisions at each density. Studies of supercritical solvation and relaxation at high pressure and temperature are enabled by this methodology.

Simultaneous CO concentration and temperature measurements using tunable diode laser absorption spectroscopy near 2.3 μm

NASA Astrophysics Data System (ADS)

Sane, Anup; Satija, Aman; Lucht, Robert P.; Gore, Jay P.

2014-10-01

Simultaneous measurements of carbon monoxide (CO) mole fraction and temperature using tunable diode laser absorption spectroscopy (TDLAS) near 2.3 μm are reported. The measurement method uses ro-vibrational transitions [R(27): v″ = 1 → v' = 3] and [R(6): v″ = 0 → v' = 2] in the first overtone band of CO near 2.3 μm (~4,278 cm-1). The measurements were performed in the post flame environment of fuel rich premixed ethylene-air flames with a N2 co-flow, stabilized over a water cooled McKenna burner. Non-uniformity in the temperature and CO mole fraction, along the absorption line of sight, in the mixing layer of the co-flow, was considered during data analysis. The TDLAS based temperature measurements (±80 K) were in good agreement with those obtained using N2 vibrational coherent anti-Stokes Raman scattering (±20 K), and the CO mole fraction measurements were in good agreement with the equilibrium values, for equivalence ratios lower than 1.8. A signal to noise ratio of 45 was achieved at an equivalence ratio of 1 for a CO concentration of 0.8 % at 1,854 K.

Broadening of spectral lines of CO2, N2O , H2CO, HCN, and H2S by pressure of gases dominant in planetary atmospheres (H2, He and CO2)

NASA Astrophysics Data System (ADS)

Samuels, Shanelle; Gordon, Iouli; Tan, Yan

2018-01-01

HITRAN1,2 is a compilation of spectroscopic parameters that a variety of computer codes use to predict and simulate the transmission and emission of light in planetary atmospheres. The goal of this project is to add to the potential of the HITRAN database towards the exploration of the planetary atmospheres by including parameters describing broadening of spectral lines by H2, CO2, and He. These spectroscopic data are very important for the study of the hydrogen and helium-rich atmospheres of gas giants as well as rocky planets with volcanic activities, including Venus and Mars, since their atmospheres are dominated by CO2. First step in this direction was accomplished by Wilzewski et al.3 where this was done for SO2, NH3, HF, HCl, OCS and C2H2. The molecules investigated in this work were CO2, N2O, H2CO, HCN and H2S. Line-broadening coefficients, line shifts and temperature-dependence exponents for transitions of these molecules perturbed by H2, CO2 and He have been assembled from available peer-reviewed experimental and theoretical sources. The data was evaluated and the database was populated with these data and their extrapolations/interpolations using semi-empirical models that were developed to this end.Acknowledgements: Financial support from NASA PDART grant NNX16AG51G and the Smithsonian Astrophysical Observatory Latino Initiative Program from the Latino Initiatives Pool, administered by the Smithsonian Latino Center is gratefully acknowledged.References: 1. HITRAN online http://hitran.org/2. Gordon, I.E., Rothman, L.S., Hill, C., Kochanov, R.V., Tan, Y., et al., 2017. The HITRAN2016 Molecular Spectroscopic Database. J. Quant. Spectrosc. Radiat. Transf. doi:10.1016/j.jqsrt.2017.06.0383. Wilzewski, J.S., Gordon, I.E., Kochanov, R. V., Hill, C., Rothman, L.S., 2016. H2, He, and CO2 line-broadening coefficients, pressure shifts and temperature-dependence exponents for the HITRAN database. Part 1: SO2, NH3, HF, HCl, OCS and C2H2. J. Quant. Spectrosc. Radiat

Variational Calculations of Ro-Vibrational Energy Levels and Transition Intensities for Tetratomic Molecules

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

A description is given of an algorithm for computing ro-vibrational energy levels for tetratomic molecules. The expressions required for evaluating transition intensities are also given. The variational principle is used to determine the energy levels and the kinetic energy operator is simple and evaluated exactly. The computational procedure is split up into the determination of one dimensional radial basis functions, the computation of a contracted rotational-bending basis, followed by a final variational step coupling all degrees of freedom. An angular basis is proposed whereby the rotational-bending contraction takes place in three steps. Angular matrix elements of the potential are evaluated by expansion in terms of a suitable basis and the angular integrals are given in a factorized form which simplifies their evaluation. The basis functions in the final variational step have the full permutation symmetries of the identical particles. Sample results are given for HCCH and BH3.

HITRAN2016: Part I. Line lists for H_2O, CO_2, O_3, N_2O, CO, CH_4, and O_2

NASA Astrophysics Data System (ADS)

Gordon, Iouli E.; Rothman, Laurence S.; Tan, Yan; Kochanov, Roman V.; Hill, Christian

2017-06-01

The HITRAN2016 database is now officially released. Plethora of experimental and theoretical molecular spectroscopic data were collected, evaluated and vetted before compiling the new edition of the database. The database is now distributed through the dynamic user interface HITRANonline (available at www.hitran.org) which offers many flexible options for browsing and downloading the data. In addition HITRAN Application Programming Interface (HAPI) offers modern ways to download the HITRAN data and use it to carry out sophisticated calculations. The line-by-line lists for almost all of the 47 HITRAN molecules were updated in comparison with the previous compilation (HITRAN2012. Some of the most important updates for major atmospheric absorbers, such as H_2O, CO_2, O_3, N_2O, CO, CH_4, and O_2, will be presented in this talk, while the trace gases will be presented in the next talk by Y. Tan. The HITRAN2016 database now provides alternative line-shape representations for a number of molecules, as well as broadening by gases dominant in planetary atmospheres. In addition, substantial extension and improvement of cross-section data is featured, which will be described in a dedicated talk by R. V. Kochanov. The new edition of the database is a substantial step forward to improve retrievals of the planetary atmospheric constituents in comparison with previous editions, while offering new ways of working with the data. The HITRAN database is supported by the NASA AURA and PDART program grants NNX14AI55G and NNX16AG51G. I. E. Gordon, L. S. Rothman, C. Hill, R. V. Kochanov, Y. Tan, et al. The HITRAN2016 Molecular Spectroscopic Database. JQSRT 2017;submitted. Many spectroscopists and atmospheric scientists worldwide have contributed data to the database or provided invaluable validations. C. Hill, I. E. Gordon, R. V. Kochanov, L. Barrett, J.S. Wilzewski, L.S. Rothman, JQSRT. 177 (2016) 4-14 R.V. Kochanov, I. E. Gordon, L. S. Rothman, P. Wcislo, C. Hill, J. S. Wilzewski

New metallicity calibration for Seyfert 2 galaxies based on the N2O2 index

NASA Astrophysics Data System (ADS)

Castro, C. S.; Dors, O. L.; Cardaci, M. V.; Hägele, G. F.

2017-05-01

We derive a new relation between the metallicity of Seyfert 2 active galactic nuclei (AGNs) and the intensity of the narrow emission-lines ratio N2O2 = log([N II] λ6584/[O II] λ3727). The calibration of this relation was performed by determining the metallicity (Z) of a sample of 58 AGNs through a diagram containing the observational data and the results of a grid of photoionization models obtained with the cloudy code. We find the new Z/Z⊙-N2O2 relation using the obtained metallicity values and the corresponding observational emission-line intensities for each object of the sample. Estimations derived through the use of this new calibration indicate that the narrow-line regions of Seyfert 2 galaxies exhibit a large range of metallicities (0.3 ≲ Z/Z⊙ ≲ 2.0), with a median value Z ≈ Z⊙. Regarding the possible existence of correlations between the luminosity L(Hβ), the electron density and the colour excess E(B - V) with the metallicity in this kind of objects, we do not find correlations between them.

O2 Herzberg State Reaction with N2: A Possible Source of Stratospheric N2O

NASA Technical Reports Server (NTRS)

Slanger, Tom G.; Copeland, Richard A.

1997-01-01

The goal of this one-year investigation was to determine whether N2O is formed in atmospherically significant quantities by the reaction of vibrationally excited levels of the O2((A3 Sigma(sub u)(sup +)) state with nitrogen. O2(A3 Sigma(sub u)(sup +)) is made throughout the upper stratosphere in considerable amounts by solar photoabsorption, and only a very small reactive yield is necessary for this mechanism to be a major N2O source. By long-term 245-252 nm irradiation of O2/N2 mixtures on- and off-resonance with absorption lines in the O2(A3 Sigma(sub u)(sup +) - X3 Sigma(sub g)(sup -)) transition, followed by N2O analysis by frequency-modulated diode laser absorption spectroscopy, we determined an upper limit for the N2O yield of the candidate reaction. This limit, 3 x 10(exp -5), eliminates O2(A3 Sigma(sub u)(sup +)) + N2 as a significant channel for the generation of stratospheric N2O. In further measurements, we established that N2O is stable under our photolysis conditions, showing that the small amounts of ozone generated from the reaction of O2(A) and O2 do not indirectly lead to destruction of N2O.

Laboratory Measurements of SO2 and N2 Absorption Spectra for Planetary Atmospheres

NASA Technical Reports Server (NTRS)

Stark, Glenn

2003-01-01

This laboratory project focuses on the following topics: 1) Measurement of SO2 ultraviolet absorption cross sections; and 2) N2 band and Line Oscillator Strengths and Line Widths in the 80 to 100 nm region. Accomplishments for these projects are summarized.

EMPIRICAL DETERMINATION OF EINSTEIN A-COEFFICIENT RATIOS OF BRIGHT [Fe II] LINES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Giannini, T.; Antoniucci, S.; Nisini, B.

The Einstein spontaneous rates (A-coefficients) of Fe{sup +} lines have been computed by several authors with results that differ from each other by up to 40%. Consequently, models for line emissivities suffer from uncertainties that in turn affect the determination of the physical conditions at the base of line excitation. We provide an empirical determination of the A-coefficient ratios of bright [Fe II] lines that would represent both a valid benchmark for theoretical computations and a reference for the physical interpretation of the observed lines. With the ESO-Very Large Telescope X-shooter instrument between 3000 Å and 24700 Å, we obtainedmore » a spectrum of the bright Herbig-Haro object HH 1. We detect around 100 [Fe II] lines, some of which with a signal-to-noise ratios ≥100. Among these latter lines, we selected those emitted by the same level, whose dereddened intensity ratios are direct functions of the Einstein A-coefficient ratios. From the same X-shooter spectrum, we got an accurate estimate of the extinction toward HH 1 through intensity ratios of atomic species, H I  recombination lines and H{sub 2} ro-vibrational transitions. We provide seven reliable A-coefficient ratios between bright [Fe II] lines, which are compared with the literature determinations. In particular, the A-coefficient ratios involving the brightest near-infrared lines (λ12570/λ16440 and λ13209/λ16440) are in better agreement with the predictions by the Quinet et al. relativistic Hartree-Fock model. However, none of the theoretical models predict A-coefficient ratios in agreement with all of our determinations. We also show that literature data of near-infrared intensity ratios better agree with our determinations than with theoretical expectations.« less

Intracellular Ca2+ concentration in the N1E-115 neuronal cell line and its use for peripheric nerve regeneration.

PubMed

Rodrigues, J M; Luís, A L; Lobato, J V; Pinto, M V; Faustino, A; Hussain, N Sooraj; Lopes, M A; Veloso, A P; Freitas, M; Geuna, S; Santos, J D; Maurício, A C

2005-01-01

Entubulation repair of peripheral nerve injuries has a lengthy history. Several experimental and clinical studies have explored the effectiveness of many biodegradable and non-degradable tubes with or without addition of molecules and cells. The main objective of the present study was to develop an economical and also an easy way for culturing a neural cell line which is capable of growing, differentiating and producing locally nerve growth factors, that are otherwise extremely expensive, inside 90 PLA/10 PLG nerve guides. For this purpose the authors have chosen the N1E-115 cell line, a clone of cells derived from mouse neuroblastoma C-1300 with the perspective of using this differentiated cellular system to cover the inside of 90 PLA/10 PLG nerve guides placed to bridge a nerve gap of 10 mm in the rat sciatic nerve experimental model. The N1E-115 cells proliferate in normal culture medium but undergo neuronal differentiation in response to DMSO. Upon induction of differentiation, proliferation of N1E-115 cells ceases, extensive neurite outgrowth is observed and the membranes become highly excitable. While it is known that Ca2+ serves as an important intracellular signal for cellular various processes, such as growth and differentiation, be toxic to cells and be involved in the triggering of events leading to excitotoxic cell death in neurons. The [Ca2+]i in non-differentiated N1E-115 cells and after distinct periods of differentiation, have been determined by the epifluorescence technique using the Fura-2-AM probe. The results of this quantitative assessment, revealed that N1E-115 cells which undergo neuronal differentiation for 48 hours in the presence of 1.5% DMSO are best qualified to be used to cover the interior of the nerve guides since the [Ca2+]i was not found to be elevated indicating thus that the onset the cell death processes was not occurred.

The CO2 absorption spectrum in the 2.3 μm transparency window by high sensitivity CRDS: (II) Self-absorption continuum

NASA Astrophysics Data System (ADS)

Mondelain, D.; Vasilchenko, S.; Čermák, P.; Kassi, S.; Campargue, A.

2017-01-01

The CO2 absorption continuum near 2.3 μm is determined for a series of sub atmospheric pressures (250-750 Torr) by high sensitivity Cavity Ring Down Spectroscopy. An experimental procedure consisting in injecting successively a gas flow of CO2 and synthetic air, keeping constant the gas pressure in the CRDS cell, has been developed. This procedure insures a high stability of the spectra baseline by avoiding changes of the optical alignment due to pressure changes. The CO2 continuum was obtained as the difference between the CO2 absorption coefficient and a local lines simulation using a Voigt profile truncated at ±25 cm-1. Following the results of the preceding analysis of the CO2 rovibrational lines (Vasilchenko S et al. J Quant Spectrosc Radiat Transfer 10.1016/j.jqsrt.2016.07.002, a CO2 line list with intensities obtained by variational calculations and empirical line positions was preferred to the HITRAN line list. A quadratic pressure dependence of the absorption continuum is observed, with an average binary absorption coefficient increasing from 2 to 4×10-8 cm-1 amagat-2 between 4320 and 4380 cm-1. The obtained continuum is found in good agreement with a previous measurement using much higher densities (20 amagat) and a low resolution grating spectrograph and is consistent with values currently used in the analysis of Venus spectra.

Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adam, Ahmad Y.; Jensen, Per, E-mail: jensen@uni-wuppertal.de; Yachmenev, Andrey

2015-12-28

We present the first variational calculation of the isotropic hyperfine coupling constant of the carbon-13 atom in the CH{sub 3} radical for temperatures T = 0, 96, and 300 K. It is based on a newly calculated high level ab initio potential energy surface and hyperfine coupling constant surface of CH{sub 3} in the ground electronic state. The ro-vibrational energy levels, expectation values for the coupling constant, and its temperature dependence were calculated variationally by using the methods implemented in the computer program TROVE. Vibrational energies and vibrational and temperature effects for coupling constant are found to be in verymore » good agreement with the available experimental data. We found, in agreement with previous studies, that the vibrational effects constitute about 44% of the constant’s equilibrium value, originating mainly from the large amplitude out-of-plane bending motion and that the temperature effects play a minor role.« less

Saturated CO{sub 2} absorption near 1.6 μm for kilohertz-accuracy transition frequencies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burkart, Johannes, E-mail: johannes.burkart@ujf-grenoble.fr; Romanini, Daniele; Campargue, Alain

2015-05-21

Doppler-free saturated-absorption Lamb dips were measured on weak rovibrational lines of {sup 12}C{sup 16}O{sub 2} between 6189 and 6215 cm{sup −1} at sub-Pa pressures using optical feedback frequency stabilized cavity ring-down spectroscopy. By referencing the laser source to an optical frequency comb, transition frequencies for ten lines of the 30013←00001 band P-branch and two lines of the 31113←01101 hot band R-branch were determined with an accuracy of a few parts in 10{sup 11}. Involving rotational quantum numbers up to 42, the data were used for improving the upper level spectroscopic constants. These results provide a highly accurate reference frequency gridmore » over the spectral interval from 1599 to 1616 nm.« less

Laboratory studies of methane near 2 μ m

NASA Astrophysics Data System (ADS)

Robert, O.; Hilico, J. C.; Loete, M.; Brown, L. R.; Pine, A. S.

2000-12-01

The 2 μ m region is a ``window" region for planets and stars abundant in methane. Characterizing the methane absorptions requires that a large number of vibration-rotation states be studied. The rovibrational levels in methane are grouped in vibrational polyads. The absorption from the three first polyads of methane (ground state: <= 10 μ m, dyad: 5--10 μ m, pentad: 3--5 μ m) are well understood and can be predicted using quantum mechanical models. Two higher polyads must be modeled to describe the 2 μ m window. The polyad called the octad has eight vibrational states in the 2--3 μ m interval. The next polyad (tetradecad) observed in the range 1.6--2 μ m is composed of 14 vibrational levels. The analyses of these two polyads have been undertaken at Dijon using high--quality FTIR spectra recorded at Kitt Peak National Observatory. The analysis of the octad was helped by spectra of the Q-branch regions of the 3ν 4 and ν2+2ν4 bands recorded at 80 K at NIST. The theoretical background for modeling rovibrational energy levels and corresponding transitions has been developed at Dijon. The analysis of the COMPLETE octad was performed for J <= 16 with a Hamiltonian containing 253 adjustable parameters (for 8 bands and 24 subbands). Nearly 8000 lines in the octad were assigned and reproduced with a standard deviation of 0.044 cm-1. Intensities were also modeled to 16% for some 2500 transitions. A prediction of some 57000 methane transitions in HITRAN format is available (from Brown). The analysis of the tetradecad system led to the assignment of nearly 200 lines of 4ν 4 band around 1.9 μ m, yielding a standard deviation of 0.180 cm-1, and to nearly 300 lines of 2ν 2+ν_3 around 1.7 μ m, yielding a standard deviation of 0.270 cm-1. Intensities are being measured. The spectral simulation is in progress near 1.8 μ m where maximum complication occurs. Part of the research reported in this paper was performed at the Jet Propulsion Laboratory, California Institute

Gas temperature determination of non-thermal atmospheric plasmas from the collisional broadening of argon atomic emission lines

NASA Astrophysics Data System (ADS)

Rodero, A.; García, M. C.

2017-09-01

In this work we propose a new method allowing gas temperature determination in argon non-thermal plasma jets, based on the measurement of the collisional broadening of different argon atomic lines corresponding to transitions into both resonance levels s2 and s4 of the 3p54s configuration. The method was developed for fourteen lines: Ar I 978.45, 935.42, 922.45, 852.14, 840.82, 826.45, 750.39 (corresponding to transitions falling to level s2) and 965.77, 842.46, 810.37, 800.62, 751.46, 738.40, 727.29 nm (corresponding to transitions falling to level s4). A carefully study of the relative importance of all broadening mechanisms to the whole profile for these lines, under a broad range of experimental conditions, revealed that for electron densities and gas temperature lower than 1015 cm-3 and 2000 K, the Stark and Doppler broadenings can be neglected in the method, but the van der Waals contribution should not be ever discarded for gas temperature determination. The gas temperature of a microwave non-thermal plasma jet was determined using nine of these lines. Results were consistent with each other, and with those obtained from the rotational temperature derived from OH ro-vibrational band. Also, the influence of the air entrance on the collisional broadening of the lines has been studied and the way the method should be modified to include this effect is indicated.

First on-line isotopic characterization of N2O above intensively managed grassland

NASA Astrophysics Data System (ADS)

Wolf, B.; Merbold, L.; Decock, C.; Tuzson, B.; Harris, E.; Six, J.; Emmenegger, L.; Mohn, J.

2015-04-01

The analysis of the four main isotopic N2O species (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) and especially the intramolecular distribution of 15N ("site preference", SP) has been suggested as a tool to distinguish source processes and to help constrain the global N2O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass-spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows the selective high-precision analysis of N2O isotopic species at trace levels and is suitable for in situ measurements. Here, we present results from the first field campaign, conducted on an intensively managed grassland site in central Switzerland. N2O mole fractions and isotopic composition were determined in the atmospheric surface layer (at 2.2 m height) at a high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N2O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11‰ for δ15Nα, δ15Nβ and δ18O, respectively. Simultaneous eddy-covariance N2O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N2O. Our measurements indicate that, in general, nitrifier-denitrification and denitrification were the prevalent sources of N2O during the campaign and that variations in isotopic composition were due to alterations in the extent to which N2O was reduced to N2 rather than to other pathways, such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intramolecular 15N site preference (SP), δ15Nbulk and δ18O, suggesting that nitrifier-denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. The flux

Line Profile of H Lyman-Beta Emission from Dissociative Excitation of H2

NASA Technical Reports Server (NTRS)

Ajello, Joseph M.; Ahmed, Syed M.; Liu, Xian-Ming

1996-01-01

A high-resolution ultraviolet spectrometer was employed for a measurement of the H Lyman-Beta(H L(sub Beta)) emission Doppler line profile at 1025.7 A from dissociative excitation of H2 by electron impact. Analysis of the deconvolved line profile reveals the existence of a narrow central peak, less than 30 mA full width at half maximum (FWHM), and a broad pedestal base about 260 mA FWHM. Analysis of the red wing of the line profile is complicated by a group of Wemer and Lyman rotational lines 160-220 mA from the line center. Analysis of the blue wing of the line profile gives the kinetic-energy distribution. There are two main kinetic-energy components to the H(3p) distribution: (1) a slow distribution with a peak value near 0 eV from singly excited states, and (2) a fast distribution with a peak contribution near 7 eV from doubly excited states. Using two different techniques, the absolute cross section of H L(sub Beta)p is found to be 3.2+/-.8 x 10(exp -19)sq cm at 100-eV electron impact energy. The experimental cross-section and line-profile results can be compared to previous studies of H(alpha) (6563.7 A) for principal quantum number n=3 and L(sub alpha)(1215.7 A) for n=2.

An Accurate Potential Energy Surface for H2O

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

In vitro cytotoxicity and differential cellular sensitivity of derivatives of diamino acids. II. N1-methyl, N1-allyl, N1-(2-chloroethyl) and N1-propargyl nitrosoureas.

PubMed

Dulude, H; Salvador, R; Gallant, G

1995-01-01

The in vitro cytotoxicity and differential cellular sensitivity of a series of new N1-methyl, N1-allyl, N1-2-chloroethyl and N1-propargyl nitrosourea derivatives of diamino acids were determined in the National Cancer Institute's primary antitumor drug screen. The compounds tested showed an in vitro anticancer activity similar to commercialized nitrosoureas such as CCNU, BCNU, MeCCNU, chlorozotocin, streptozotocin and PCNU. The alkylating moiety of the nitrosoureas seems to play a role in the general selectivity of our compounds. The N1-methyl and N1-2-chloroethyl nitrosourea derivatives are more selective for central nervous system cell lines, the N1-allyl nitrosourea derivatives are more selective for lung cancer cell lines and the N1-propargyl nitrosoureas are more selective for leukemia cell lines.

Isotopic and quantum-rovibrational-state effects for the ion-molecule reaction in the collision energy range of 0.03-10.00 eV.

PubMed

Xu, Yuntao; Xiong, Bo; Chang, Yih Chung; Ng, C Y

2017-03-29

We report detailed quantum-rovibrational-state-selected integral cross sections for the formation of H 3 O + via H-transfer (σ HT ) and H 2 DO + via D-transfer (σ DT ) from the reaction in the center-of-mass collision energy (E cm ) range of 0.03-10.00 eV, where (vvv) = (000), (100), and (020) and . The E cm inhibition and rotational enhancement observed for these reactions at E cm < 0.5 eV are generally consistent with those reported previously for H 2 O + + H 2 (D 2 ) reactions. However, in contrast to the vibrational inhibition observed for the latter reactions at low E cm < 0.5 eV, both the σ HT and σ DT for the H 2 O + + HD reaction are found to be enhanced by (100) vibrational excitation, which is not predicted by the current state-of-the-art theoretical dynamics calculations. Furthermore, the (100) vibrational enhancement for the H 2 O + + HD reaction is observed in the full E cm range of 0.03-10.00 eV. The fact that vibrational enhancement is only observed for the reaction of H 2 O + + HD, and not for H 2 O + + H 2 (D 2 ) reactions suggests that the asymmetry of HD may play a role in the reaction dynamics. In addition to the strong isotopic effect favoring the σ HT channel of the H 2 O + + HD reaction at low E cm < 0.5 eV, competition between the σ HT and σ DT of the H 2 O + + HD reaction is also observed at E cm = 0.3-10.0 eV. The present state-selected study of the H 2 O + + HD reaction, along with the previous studies of the H 2 O + + H 2 (D 2 ) reactions, clearly shows that the chemical reactivity of H 2 O + toward H 2 (HD, D 2 ) depends not only on E cm , but also on the rotational and vibrational states of H 2 O + (X 2 B 1 ). The detailed σ HT and σ DT values obtained here with single rovibrational-state selections of the reactant H 2 O + are expected to be valuable benchmarks for state-of-the-art theoretical calculations on the chemical dynamics of the title reaction.

Molecular association of 2-(n-alkylamino)-1,4-naphthoquinone derivatives: Electrochemical, DFT studies and antiproliferative activity against leukemia cell lines

NASA Astrophysics Data System (ADS)

Patil, Rishikesh; Bhand, Sujit; Konkimalla, V. Badireenath; Banerjee, Priyabrata; Ugale, Bharat; Chadar, Dattatray; Saha, Sourav Kr.; Praharaj, Prakash Priyadarshi; Nagaraja, C. M.; Chakrovarty, Debamitra; Salunke-Gawali, Sunita

2016-12-01

Molecular structures and their molecular association of 2-(n-alkylamino)-1,4-naphthoquinone, viz., LH-3; propyl, LH-4; butyl and LH-8; octyl derivatives were studied by single crystal X-ray diffraction studies. Synthesis and characterization of 2-octylamino-1,4-naphthoquinone; LH-8 was discussed. The molecule of LH-3 crystallizes in orthorhombic space group P21/c, while the LH-4 and LH-8 molecule crystallizes in triclinic space group P-1. LH-3, LH-4 and LH-8 showed intermolecular N-H⋯O and C-H⋯O interactions, LH-3 showed unique C(3)-H(3)⋯O(1) interaction. Interchain π-π stacking, slipped π-π stacking and C⋯O close contacts was respectively observed in LH-3, LH-4 and LH-8. Electrochemical studies were performed on first eight members of homologous series of 2-(n-alkylamino)-1,4-naphthoquinone (LH-1 to LH-8) by cyclic voltammetry. Naphthoquinone to naphthosemiquinone reversible redox couple was observed in all compounds ∼ E1/2 = -0.657 ± 0.05 V. HOMO-LUMO band gap was determined for the neutral form as well as the monoanionic radical form viz. naphthosemiquinone form of selected derivatives by DFT studies. It has been observed that the electron density is delocalized in the naphthoquinone ring in both neutral as well as one electron reduced form of compounds. Antiproliferative activity of LH-1 to LH-8 was evaluated against two cancer cell lines, THP1(acute monocytic leukemia) and K562(human immortalized myelogenous leukemia cell line) cells. It was observed that, in THP1 cells, compounds LH-2 and LH-3 are very active while LH-1, LH-4 and LH-6 were moderately active and LH-5, LH-7 and LH-8 were totally inactive. Contrastingly, in K562 cells all of the compounds were moderately active.

Comparison of the usefulness of the CACO-2 cell line with standard substrates for isolation of swine influenza A viruses.

PubMed

Chiapponi, Chiara; Zanni, Irene; Garbarino, Chiara; Barigazzi, Giuseppe; Foni, Emanuela

2010-01-01

Influenza A virus isolation is undertaken routinely in embryonated chicken eggs, but to improve virus detection various cell lines can be used. The CACO-2 cell line was compared to the MDCK cell line and embryonated chicken eggs for the isolation of H1N1, H1N2, H3N2 swine influenza A virus subtypes from clinical specimens. From 2006 to 2008, 104 influenza A samples found positive by PCR from 42 respiratory outbreaks in Italian swine farms were examined by virus isolation. Sixty swine influenza A viruses were isolated (16 H1N1, 28 H1N2 and 16 H3N2) and their growth behaviour on the different substrates was examined. 16/16 H1N1, 28/28 H1N2 and 8/16 of H3N2 viruses were isolated from the CACO-2 cell line, while 7/16 H1N1, 3/28 H1N2 and 16/16 H3N2 viruses were isolated using embryonated chicken eggs. Only 9/16 H1N1, 1/28 H1N2 and 6/16 H3N2 viruses replicated in MDCK cells. A link was found between viral hemagglutinin and the isolation rate on the various substrates. The CACO-2 line was statistically more sensitive (Fisher's exact test, p<0.01) compared to the MDCK cells and embryonated chicken eggs for the isolation of H1N1 and H1N2 subtypes. In contrast influenza A H3N2 virus was isolated more readily in embryonated chicken eggs than in cultured cells (Fisher's exact test, p<0.01).

High resolution FTIR spectroscopic study of the ν4 band of CH 3CHF 2 enclosed in a flow of cold N 2 gas

NASA Astrophysics Data System (ADS)

Appadoo, Dominique R. T.; Robertson, Evan G.; McNaughton, Don

2003-01-01

An enclosive flow cooling (EFC) cell has been constructed, and coupled to a Brüker IFS 120HR high resolution Fourier transform spectrometer to record rotationally cold absorption spectra of gases of atmospheric interest at high spectral resolution. The new system has been characterized using N 2O, revealing that rotational temperatures as cold as 110 K are readily attainable using liquid nitrogen as a cryogen. Infrared spectra of the ν4 band of 1,1-difluoroethane (R152a), CH 3CHF 2, cooled in the EFC cell have been measured at a resolution of 0.0019 cm-1. Eight hundred and twenty rovibrational transitions of the weak ν4 band with 2⩽ J'⩽46 and Kc'⩽16 were assigned and fitted to Watson's A-reduced Hamiltonian. The ν4 CH 3 symmetric deformation ( a/c-type) was found to be coupled to the ν13 asymmetric deformation ( b-type) via an a-axis Coriolis interaction. In the ensuing analysis, values of spectroscopic constants were obtained for both the ν4 and dark ν13 states. Supporting ab initio calculations up to the MP2/TZV+(3 df,3 p) level are presented.

SO_2 Absorption Cross Sections and N_2 VUV Oscillator Strengths for Planetary Atmosphere Studies

NASA Astrophysics Data System (ADS)

Smith, Peter L.; Stark, G.; Rufus, J.; Pickering, J. C.; Cox, G.; Huber, K. P.

1998-09-01

The determination of the chemical composition of the atmosphere of Io from Hubble Space Telescope observations in the 190-220 nm wavelength region requires knowledge of the photoabsorption cross sections of SO_2 at temperatures ranging from about 110 K to 300 K. We are engaged in a laboratory program to measure SO_2 absorption cross sections with very high resolving power (lambda /delta lambda =~ 450,000) and at a range of temperatures appropriate to the Io atmosphere. Previous photoabsorption measurements, with lambda /delta lambda =~ 100,000, have been unable to resolve the very congested SO_2 spectrum, and, thus, to elucidate the temperature dependence of the cross sections. Our measurements are being performed at Imperial College, London, using an ultraviolet Fourier transform spectrometer. We will present our recently completed room temperature measurements of SO_2 cross sections in the 190-220 nm region and plans for extending these to ~ 195 K. Analyses of Voyager VUV occultation measurements of the N_2-rich atmospheres of Titan and Triton have been hampered by the lack of fundamental spectroscopic data for N_2, in particular, by the lack of reliable f-values and line widths for electronic bands of N_2 in the 80-100 nm wavelength region. We are continuing our program of measurements of band oscillator strengths for the many (approximately 100) N_2 bands between 80 and 100 nm. We report new f-values, derived from data obtained at the Photon Factory (Tsukuba, Japan) synchrotron radiation facility with lambda /delta lambda =~ 130,000, of 37 bands in the 80-86 nm region and 21 bands in the 90-95 nm region. We have also begun the compilation of a searchable archive of N_2 data on the World Wide Web; see http://cfa-www.harvard. edu/amp/data/n2/n2home.html. The archive, covering the spectroscopy of N_2 between 80 and 100 nm, will include published and unpublished (14) N_2, (14) N(15) N, and (15) N_2 line lists and spectroscopic identifications, excited state energy

Biosynthesis of N,N-dimethyltryptamine (DMT) in a melanoma cell line and its metabolization by peroxidases.

PubMed

Gomes, Melissa M; Coimbra, Janine B; Clara, Renan O; Dörr, Felipe A; Moreno, Ana Carolina R; Chagas, Jair R; Tufik, Sérgio; Pinto, Ernani; Catalani, Luiz H; Campa, Ana

2014-04-01

Tryptophan (TRP) is essential for many physiological processes, and its metabolism changes in some diseases such as infection and cancer. The most studied aspects of TRP metabolism are the kynurenine and serotonin pathways. A minor metabolic route, tryptamine and N,N-dimethyltryptamine (DMT) biosynthesis, has received far less attention, probably because of the very low amounts of these compounds detected only in some tissues, which has led them to be collectively considered as trace amines. In a previous study, we showed a metabolic interrelationship for TRP in melanoma cell lines. Here, we identified DMT and N,N-dimethyl-N-formyl-kynuramine (DMFK) in the supernatant of cultured SK-Mel-147 cells. Furthermore, when we added DMT to the cell culture, we found hydroxy-DMT (OH-DMT) and indole acetic acid (IAA) in the cell supernatant at 24 h. We found that SK-Mel-147 cells expressed mRNA for myeloperoxidase (MPO) and also had peroxidase activity. We further found that DMT oxidation was catalyzed by peroxidases. DMT oxidation by horseradish peroxidase, H2O2 and MPO from PMA-activated neutrophils produced DMFK, N,N-dimethyl-kynuramine (DMK) and OH-DMT. Oxidation of DMT by peroxidases apparently uses the common peroxidase cycle involving the native enzyme, compound I and compound II. In conclusion, this study describes a possible alternative metabolic pathway for DMT involving peroxidases that has not previously been described in humans and identifies DMT and metabolites in a melanoma cell line. The extension of these findings to other cell types and the biological effects of DMT and its metabolites on cell proliferation and function are key questions for future studies. Copyright © 2014 Elsevier Inc. All rights reserved.

Fixed node diffusion Monte Carlo using a genetic algorithm: a study of the CO-(4)He(N) complex, N = 1…10.

PubMed

Ramilowski, Jordan A; Farrelly, David

2012-06-14

The diffusion Monte Carlo (DMC) method is a widely used algorithm for computing both ground and excited states of many-particle systems; for states without nodes the algorithm is numerically exact. In the presence of nodes approximations must be introduced, for example, the fixed-node approximation. Recently we have developed a genetic algorithm (GA) based approach which allows the computation of nodal surfaces on-the-fly [Ramilowski and Farrelly, Phys. Chem. Chem. Phys., 2010, 12, 12450]. Here GA-DMC is applied to the computation of rovibrational states of CO-(4)He(N) complexes with N≤ 10. These complexes have been the subject of recent high resolution microwave and millimeter-wave studies which traced the onset of microscopic superfluidity in a doped (4)He droplet, one atom at a time, up to N = 10 [Surin et al., Phys. Rev. Lett., 2008, 101, 233401; Raston et al., Phys. Chem. Chem. Phys., 2010, 12, 8260]. The frequencies of the a-type (microwave) series, which correlate with end-over-end rotation in the CO-(4)He dimer, decrease from N = 1 to 3 and then smoothly increase. This signifies the transition from a molecular complex to a quantum solvated system. The frequencies of the b-type (millimeter-wave) series, which evolves from free rotation of the rigid CO molecule, initially increase from N = 0 to N∼ 6 before starting to decrease with increasing N. An interesting feature of the b-type series, originally observed in the high resolution infra-red (IR) experiments of Tang and McKellar [J. Chem. Phys., 2003, 119, 754] is that, for N = 7, two lines are observed. The GA-DMC algorithm is found to be in good agreement with experimental results and possibly detects the small (∼0.7 cm(-1)) splitting in the b-series line at N = 7. Advantages and disadvantages of GA-DMC are discussed.

Ab initio state-specific N2 + O dissociation and exchange modeling for molecular simulations

NASA Astrophysics Data System (ADS)

Luo, Han; Kulakhmetov, Marat; Alexeenko, Alina

2017-02-01

Quasi-classical trajectory (QCT) calculations are used in this work to calculate state-specific N2(X1Σ ) +O(3P ) →2 N(4S ) +O(3P ) dissociation and N2(X1Σ ) +O(3P ) →NO(X2Π ) +N(4S ) exchange cross sections and rates based on the 13A″ and 13A' ab initio potential energy surface by Gamallo et al. [J. Chem. Phys. 119, 2545-2556 (2003)]. The calculations consider translational energies up to 23 eV and temperatures between 1000 K and 20 000 K. Vibrational favoring is observed for dissociation reaction at the whole range of collision energies and for exchange reaction around the dissociation limit. For the same collision energy, cross sections for v = 30 are 4 to 6 times larger than those for the ground state. The exchange reaction has an effective activation energy that is dependent on the initial rovibrational level, which is different from dissociation reaction. In addition, the exchange cross sections have a maximum when the total collision energy (TCE) approaches dissociation energy. The calculations are used to generate compact QCT-derived state-specific dissociation (QCT-SSD) and QCT-derived state-specific exchange (QCT-SSE) models, which describe over 1 × 106 cross sections with about 150 model parameters. The models can be used directly within direct simulation Monte Carlo and computational fluid dynamics simulations. Rate constants predicted by the new models are compared to the experimental measurements, direct QCT calculations and predictions by other models that include: TCE model, Bose-Candler QCT-based exchange model, Macheret-Fridman dissociation model, Macheret's exchange model, and Park's two-temperature model. The new models match QCT-calculated and experimental rates within 30% under nonequilibrium conditions while other models under predict by over an order of magnitude under vibrationally-cold conditions.

High-resolution synchrotron FTIR spectroscopic analysis of the Coriolis interaction between the v10 = 1 and v8 = 1 states of ethylene-cis-1,2-d2

NASA Astrophysics Data System (ADS)

Ng, L. L.; Tan, T. L.; Wong, Andy; Appadoo, Dominique R. T.; McNaughton, Don

2016-10-01

The synchrotron Fourier transform infrared (FTIR) spectrum of the b-type ν10 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at a resolution of 0.00096 cm-1 in the 550-750 cm-1 region. The measured FWHM of the lines was about 0.002 cm-1. The ν10 band, centred at 662.871885(27) cm-1 was found to be perturbed through a b-type Coriolis resonance with the infrared inactive ν8 at 759.9582(20) cm-1. In this work, 1989 infrared transitions of ν10 were assigned for the first time. These perturbed and unperturbed infrared transitions were fitted with an rms deviation of 0.00033 cm-1 using the Watson's A-reduced Hamiltonian in the Ir representation with three Coriolis terms to derive the rovibrational constants for v10 = 1 and v8 = 1 states. Ground state rovibrational constants up to two sextic terms were also derived from a fit of a total of 2532 ground state combination differences with arms deviation of 0.00030 cm-1 from the infrared transitions of the present analysis and those determined previously. The ground state constants compared favourably to the equilibrium state constants from harmonic cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels. The rotational constants of ν10 and ν8 from this work agree well with those from anharmonic calculations.

Spatial variation of the cooling lines in the reflection nebula NGC 7023

NASA Astrophysics Data System (ADS)

Bernard-Salas, J.; Habart, E.; Köhler, M.; Abergel, A.; Arab, H.; Lebouteiller, V.; Pinto, C.; van der Wiel, M. H. D.; White, G. J.; Hoffmann, M.

2015-02-01

Context. The north-west photo-dissociation region (PDR) in the reflection nebula NGC 7023 displays a complex structure. Filament-like condensations at the edge of the cloud can be traced via the emission of the main cooling lines, offering a great opportunity to study the link between the morphology and energetics of these regions. Aims: We study the spatial variation of the far-infrared fine-structure lines of [C ii] (158 μm) and [O i] (63 and 145 μm). These lines trace the local gas conditions across the PDR. We also compare their emission with molecular tracers including rotational and ro-vibrational lines of H2 and high-rotational lines of CO. Methods: We used observations from the Herschel/PACS instrument to map the spatial distribution of these fine-structure lines. The observed region covers a square area of about 110″ × 110″ with an angular resolution that varies from 4'' to 11''. We compared this emission with ground-based and Spitzer observations of H2 lines, Herschel/SPIRE observations of CO lines, and Spitzer/IRAC 3.6 μm images that trace the emission of polycyclic aromatic hydrocarbons. We used a PDR code to model the [O i]145 μm line and infer the physical conditions in the region. Results: The [C ii] (158 μm) and [O i] (63 and 145 μm) lines arise from the warm cloud surface where the PDR is located and the gas is warm, cooling the region. We find that although the relative contribution to the cooling budget over the observed region is dominated by [O i]63 μm (>30%), H2 contributes significantly in the PDR (~35%), as does [C ii]158 μm outside the PDR (30%). Other species contribute little to the cooling ([O i]145 μm 9%, and CO 4%). Enhanced emission of these far-infrared atomic lines trace the presence of condensations, where high-excitation CO rotational lines and dust emission in the submillimetre are detected as well. The [O i] maps resolve these condensations into two structures and show that the peak of [O i] is slightly displaced

Observation of photoassociation of ultracold sodium and cesium at the asymptote Na (3S1/2) + Cs (6P1/2)

NASA Astrophysics Data System (ADS)

Wu, Jizhou; Liu, Wenliang; Wang, Xiaofeng; Ma, Jie; Li, Dan; Sovkov, Vladimir B.; Xiao, Liantuan; Jia, Suotang

2018-05-01

We report on the production of ultracold heteronuclear NaCs* molecules in a dual-species magneto-optical trap through photoassociation. The electronically excited molecules are formed below the Na (3S1/2) + Cs (6P1/2) dissociation limit. 12 resonance lines are detected using trap-loss spectroscopy based on a highly sensitive modulation technique. The highest observed rovibrational level exhibits clear hyperfine structure, which is detected for the first time. This structure is simulated within a simplified model consisting of 4 coupled levels belonging to the initially unperturbed Hund's case "a" electronic states, which have been explored in our previous work that dealt with the Na (3S1/2) + Cs (6P3/2) asymptote [W. Liu et al., Phys. Rev. A 94, 032518 (2016)].

Anisotropic elastic scattering of stripe/line-shaped scatters to two-dimensional electron gas: Model and illustrations in a nonpolar AlGaN/GaN hetero-junction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jinfeng, E-mail: jfzhang@xidian.edu.cn; Li, Yao; Yan, Ran

In a semiconductor hetero-junction, the stripe/line-shaped scatters located at the hetero-interface lead to the anisotropic transport of two-dimensional electron gas (2DEG). The elastic scattering of infinitely long and uniform stripe/line-shaped scatters to 2DEG is theoretically investigated based on a general theory of anisotropic 2DEG transport [J. Schliemann and D. Loss, Phys. Rev. B 68(16), 165311 (2003)], and the resulting 2DEG mobility along the applied electrical field is modeled to be a function of the angle between the field and the scatters. The anisotropy of the scattering and the mobility originate in essence from that the stripe/line-shaped scatters act upon themore » injecting two-dimensional wave vector by changing only its component perpendicular to the scatters. Three related scattering mechanisms in a nonpolar AlGaN/GaN hetero-junction are discussed as illustrations, including the striated morphology caused interface roughness scattering, and the polarization induced line charge dipole scattering and the misfit dislocation scattering at the AlGaN/GaN interface. Different anisotropic behaviors of the mobility limited by these scattering mechanisms are demonstrated, but analysis shows that all of them are determined by the combined effects of the anisotropic bare scattering potential and the anisotropic dielectric response of the 2DEG.« less

High Resolution UV SO2 Absorption Cross Sections and VUV N2 Oscillator Strengths for Planetary Atmospheres Studies

NASA Astrophysics Data System (ADS)

Smith, P. L.; Stark, G.; Rufus, J.

2000-10-01

The determination of the chemical composition of the atmosphere of Io in the 190-220 nm wavelength region requires a knowledge of the photoabsorption cross section of SO2 at temperatures ranging from 110 to 300 K. We are continuing our laboratory program to measure SO2 absorption cross sections with very high resolving power (450,000) at a range of temperatures appropriate to the Io atmosphere. Previous photoabsorption measurements have been unable to resolve the very congested SO2 spectrum. Out measurements are being undertaken at Imperial College, London, using an ultraviolet Fourier transform spectrometer. We recently completed room temperature measurements of SO2 cross sections in the 190-220 nm region (Stark et al., JGR Planets 104, 16,585 (1999)). Current laboratory work is focusing on a complementary set of measurements at 160 K. Preliminary results will be presented. Analyses of Voyager VUV occultation measurements of the N2-rich atmospheres of Titan and Triton are hampered by the lack of fundamental spectroscopic data for N2, in particular, by the lack of reliable f-values and line widths for electronic bands of N2 in the 80-100 nm wavelength region. We are continuing our program to measure band oscillator strengths for about 100 N2 bands between 80-100 nm. We have begun an on-line molecular spectroscopic atlas [http://cfa-www.harvard.edu/amdata/ampdata/N2ARCHIVE/n2home.html]. The archive includes published and unpublished 14N2, 14N15N, and 15N2 line lists and spectroscopic identifications, excited state energy levels, band and line f-values, a summary of published band f-value and line width measurements, and a cross-referenced summary of the relevant N2 literature. The listings are searchable by wavelength interval or band identification and are suitable for down-loading in a convenient format. This work was supported in part by NASA Grant NAG5-6222 and the Smithsonian Institution Atherton Seidel Grant Program.

Cytoskeleton changes following differentiation of N1E-115 neuroblastoma cell line.

PubMed

Oh, J-E; Karlmark Raja, K; Shin, J-H; Pollak, A; Hengstschläger, M; Lubec, G

2006-10-01

No systematic approach to detect expression of differentiation-related elements was published so far. The undifferentiated N1E-115 neuroblastoma cell line was switched into a neuronal phenotype by DMSO treatment and used for proteomic experiments. We used two-dimensional gel electrophoresis followed by unambiguous mass spectrometrical identification of proteins to generate a map of cytoskeleton proteins (CPs), i.e., to search for differentiation-related structures. Alpha-actin, actin-like protein 6A, gamma-tubulin complex component 2, tubulin alpha 3/alpha 7, CLIP associating protein 2, B4 integrin interactor homolog were detectable in the undifferentiated cell line exclusively and neuron-specific CPs drebrin and presynaptic density protein 95, actin-related protein 2/3, alpha and beta-centractin, PDZ-domain actin binding protein, actinin alpha 1, profilin II, ezrin, coactosin-like protein, transgelin 2, myosin light polypeptide 6, tubulin alpha 2, 6 and 7, beta tubulin (94% similar with tubulin beta-2), tubulin beta 3, tubulin tyrosine ligase-like protein 1, lamin B1 and keratin 20 were observed in the differentiated cell line only. We herein identified differentiation-related expressional patterns thus providing new evidence for the role of CPs in the process of neuronal differentiation.

High-level theoretical rovibrational spectroscopy beyond fc-CCSD(T): The C3 molecule.

PubMed

Schröder, Benjamin; Sebald, Peter

2016-01-28

An accurate local (near-equilibrium) potential energy surface (PES) is reported for the C3 molecule in its electronic ground state (X̃(1)Σg (+)). Special care has been taken in the convergence of the potential relative to high-order correlation effects, core-valence correlation, basis set size, and scalar relativity. Based on the aforementioned PES, several rovibrational states of all (12)C and (13)C substituted isotopologues have been investigated, and spectroscopic parameters based on term energies up to J = 30 have been calculated. Available experimental vibrational term energies are reproduced to better than 1 cm(-1) and rotational constants show relative errors of not more than 0.01%. The equilibrium bond length has been determined in a mixed experimental/theoretical approach to be 1.294 07(10) Å in excellent agreement with the ab initio composite value of 1.293 97 Å. Theoretical band intensities based on a newly developed electric dipole moment function also suggest that the infrared active (1, 1(1), 0)←(0, 0(0), 0) combination band might be observable by high-resolution spectroscopy.

First on-line isotopic characterization of N2O emitted from intensively managed grassland

NASA Astrophysics Data System (ADS)

Wolf, B.; Merbold, L.; Decock, C.; Tuzson, B.; Harris, E.; Six, J.; Emmenegger, L.; Mohn, J.

2015-01-01

The analysis of the four main isotopic N2O species (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) and especially the intramolecular distribution of 15N (site preference, SP) has been suggested as a tool to distinguish source processes and to help constrain the global N2O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows selective high-precision analysis of N2O isotopic species at trace levels and is suitable for in situ measurements. Here, we present results from the first field campaign, conducted on an intensively managed grassland in central Switzerland. N2O mole fractions and isotopic composition were determined in the atmospheric surface layer (2 m height) at high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N2O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11‰ for δ15Nα, δ15Nβ and δ18O, respectively. Simultaneous eddy-covariance N2O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N2O. Our measurements indicate that in general, nitrifier-denitrification and denitrification were the prevalent sources of N2O during the campaign, and that variations in isotopic composition were rather due to alterations in the extent to which N2O was reduced to N2, than other pathways such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intra-molecular 15N site preference (SP), δ15Nbulk and δ18O, suggesting nitrifier denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. Flux-averaged isotopic composition of N

High accuracy line positions of the ν1 fundamental band of 14N216O

NASA Astrophysics Data System (ADS)

AlSaif, Bidoor; Lamperti, Marco; Gatti, Davide; Laporta, Paolo; Fermann, Martin; Farooq, Aamir; Lyulin, Oleg; Campargue, Alain; Marangoni, Marco

2018-05-01

The ν1 fundamental band of N2O is examined by a novel spectrometer that relies on the frequency locking of an external-cavity quantum cascade laser around 7.8 μm to a near-infrared Tm:based frequency comb at 1.9 μm. Due to the large tunability, nearly 70 lines in the 1240-1310 cm-1 range of the ν1 band of N2O, from P(40) to R(31), are for the first time measured with an absolute frequency calibration and an uncertainty from 62 to 180 kHz, depending on the line. Accurate values of the spectroscopic constants of the upper state are derived from a fit of the line centers (rms ≈ 4.8 × 10-6 cm-1 or 144 kHz). The ν1 transitions presently measured in a Doppler regime validate high accuracy predictions based on sub-Doppler measurements of the ν3 and ν3-ν1 transitions.

The cyclopropene radical cation: Rovibrational level structure at low energies from high-resolution photoelectron spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasilatou, K.; Michaud, J. M.; Baykusheva, D.

2014-08-14

The cyclopropene radical cation (c-C{sub 3}H{sub 4}{sup +}) is an important but poorly characterized three-membered-ring hydrocarbon. We report on a measurement of the high-resolution photoelectron and photoionization spectra of cyclopropene and several deuterated isotopomers, from which we have determined the rovibrational energy level structure of the X{sup ~+} {sup 2}B{sub 2} ground electronic state of c-C{sub 3}H{sub 4}{sup +} at low energies for the first time. The synthesis of the partially deuterated isotopomers always resulted in mixtures of several isotopomers, differing in their number of D atoms and in the location of these atoms, so that the photoelectron spectra ofmore » deuterated samples are superpositions of the spectra of several isotopomers. The rotationally resolved spectra indicate a C{sub 2v}-symmetric R{sub 0} structure for the ground electronic state of c-C{sub 3}H{sub 4}{sup +}. Two vibrational modes of c-C{sub 3}H{sub 4}{sup +} are found to have vibrational wave numbers below 300 cm{sup −1}, which is surprising for such a small cyclic hydrocarbon. The analysis of the isotopic shifts of the vibrational levels enabled the assignment of the lowest-frequency mode (fundamental wave number of ≈110 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to the CH{sub 2} torsional mode (ν{sub 8}{sup +}, A{sub 2} symmetry) and of the second-lowest-frequency mode (≈210 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to a mode combining a CH out-of-plane with a CH{sub 2} rocking motion (ν{sub 15}{sup +}, B{sub 2} symmetry). The potential energy along the CH{sub 2} torsional coordinate is flat near the equilibrium structure and leads to a pronounced anharmonicity.« less

18 CFR 2.2 - Transmission lines.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 18 Conservation of Power and Water Resources 1 2010-04-01 2010-04-01 false Transmission lines. 2.2 Section 2.2 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY GENERAL RULES GENERAL POLICY AND INTERPRETATIONS Statements of General Policy and Interpretations...

18 CFR 2.2 - Transmission lines.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 18 Conservation of Power and Water Resources 1 2012-04-01 2012-04-01 false Transmission lines. 2.2 Section 2.2 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY GENERAL RULES GENERAL POLICY AND INTERPRETATIONS Statements of General Policy and Interpretations...

18 CFR 2.2 - Transmission lines.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 18 Conservation of Power and Water Resources 1 2013-04-01 2013-04-01 false Transmission lines. 2.2 Section 2.2 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY GENERAL RULES GENERAL POLICY AND INTERPRETATIONS Statements of General Policy and Interpretations...

18 CFR 2.2 - Transmission lines.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 18 Conservation of Power and Water Resources 1 2014-04-01 2014-04-01 false Transmission lines. 2.2 Section 2.2 Conservation of Power and Water Resources FEDERAL ENERGY REGULATORY COMMISSION, DEPARTMENT OF ENERGY GENERAL RULES GENERAL POLICY AND INTERPRETATIONS Statements of General Policy and Interpretations...

AKARI Near-infrared Spectroscopy of the Extended Green Object G318.05+0.09: Detection of CO Fundamental Ro-vibrational Emission

NASA Astrophysics Data System (ADS)

Onaka, Takashi; Mori, Tamami; Sakon, Itsuki; Ardaseva, Aleksandra

2016-10-01

We present the results of near-infrared (2.5-5.4 μm) long-slit spectroscopy of the extended green object (EGO) G318.05+0.09 with AKARI. Two distinct sources are found in the slit. The brighter source has strong red continuum emission with H2O ice, CO2 ice, and CO gas and ice absorption features at 3.0, 4.25 μm, 4.67 μm, respectively, while the other greenish object shows peculiar emission that has double peaks at around 4.5 and 4.7 μm. The former source is located close to the ultra compact H II region IRAS 14498-5856 and is identified as an embedded massive young stellar object (YSO). The spectrum of the latter source can be interpreted by blueshifted (-3000 ˜ -6000 km s-1) optically thin emission of the fundamental ro-vibrational transitions (v=1{--}0) of CO molecules with temperatures of 12000-3700 K without noticeable H2 and H I emission. We discuss the nature of this source in terms of outflow associated with the young stellar object and supernova ejecta associated with a supernova remnant.

Registration of N619 to N640 grain sorghum lines with waxy or wild-type endosperm

USDA-ARS?s Scientific Manuscript database

Sorghum [Sorghum bicolor (L.) Moench] lines A N619 to A N636 (Reg. No. GS-XXX, PI 670134 to Reg. No. GS-XXX, PI 670151); B N619 to B N636 (Reg. No. GS-XXX, PI 671777 to Reg. No. GS-XXX, PI 671794); and R N637 to R N640 (Reg. No. GS-XXX, PI 670152 to Reg. No. GS-XXX, PI 670155) comprise nine pairs of...

The ortho:para-H_2 ratio in C- and J-type shocks

NASA Astrophysics Data System (ADS)

Wilgenbus, D.; Cabrit, S.; Pineau des Forêts, G.; Flower, D. R.

2000-04-01

We have computed extensive grids of models of both C- and J-type planar shock waves, propagating in dark, cold molecular clouds, in order to study systematically the behaviour of the ortho:para-H_2 ratio. Careful attention was paid to both macroscopic (dynamical) and microscopic (chemical reactions and collisional population transfer in H_2) aspects. We relate the predictions of the models to observational determinations of the ortho:para-H_2 ratio using both pure rotational lines and rovibrational lines. As an illustration, we consider ISO and ground-based H_2 observations of HH 54. Neither planar C-type nor planar J-type shocks appear able to account fully for these observations. Given the additional constraints provided by the observed ortho:para H_2 ratios, a C-type bowshock, or a C-type precursor followed by a J-type shock, remain as plausible models. Tables~2a-f and 4a-f are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/Abstract.html

Label-free LC-MS analysis of HER2+ breast cancer cell line response to HER2 inhibitor treatment.

PubMed

Di Luca, Alessio; Henry, Michael; Meleady, Paula; O'Connor, Robert

2015-08-04

Human epidermal growth-factor receptor (HER)-2 is overexpressed in 25 % of breast-cancers and is associated with an aggressive form of the disease with significantly shortened disease free and overall survival. In recent years, the use of HER2-targeted therapies, monoclonal-antibodies and small molecule tyrosine-kinase inhibitors has significantly improved the clinical outcome for HER2-positive breast-cancer patients. However, only a fraction of HER2-amplified patients will respond to therapy and the use of these treatments is often limited by tumour drug insensitivity or resistance and drug toxicities. Currently there is no way to identify likely responders or rational combinations with the potential to improve HER2-focussed treatment outcome. In order to further understand the molecular mechanisms of treatment-response with HER2-inhibitors, we used a highly-optimised and reproducible quantitative label-free LC-MS strategy to characterize the proteomes of HER2-overexpressing breast-cancer cell-lines (SKBR3, BT474 and HCC1954) in response to drug-treatment with HER2-inhibitors (lapatinib, neratinib or afatinib). Following 12 ours treatment with different HER2-inhibitors in the BT474 cell-line; compared to the untreated cells, 16 proteins changed significantly in abundance following lapatinib treatment (1 μM), 21 proteins changed significantly following neratinib treatment (150 nM) and 38 proteins changed significantly following afatinib treatment (150 nM). Whereas following 24 hours treatment with neratinib (200 nM) 46 proteins changed significantly in abundance in the HCC1954 cell-line and 23 proteins in the SKBR3 cell-line compared to the untreated cells. Analysing the data we found that, proteins like trifunctional-enzyme subunit-alpha, mitochondrial; heterogeneous nuclear ribonucleoprotein-R and lamina-associated polypeptide 2, isoform alpha were up-regulated whereas heat shock cognate 71 kDa protein was down-regulated in 3 or more comparisons. This proteomic

Production and Identification of Wheat-Agropyron cristatum 2P Translocation Lines

PubMed Central

Li, Huanhuan; Lv, Mingjie; Song, Liqiang; Zhang, Jinpeng; Gao, Ainong; Li, Lihui; Liu, Weihua

2016-01-01

Agropyron cristatum (L.) Gaertn. (2n = 28, PPPP), a wild relative of common wheat, possesses many potentially valuable traits that can be transferred to common wheat through breeding programs. The wheat-A. cristatum disomic addition and translocation lines can be used as bridge materials to introduce alien chromosomal segments to wheat. Wheat-A. cristatum 2P disomic addition line II-9-3 was highly resistant to powdery mildew and leaf rust, which was reported in our previous study. However, some translocation lines induced from II-9-3 have not been reported. In this study, some translocation lines were induced from II-9-3 by 60Co-γ irradiation and gametocidal chromosome 2C and then identified by cytological methods. Forty-nine wheat-A. cristatum translocation lines were obtained and various translcoation types were identified by GISH (genomic in situ hybridization), such as whole-arm, segmental and intercalary translocations. Dual-color FISH (fluorescent in situ hybridization) was applied to identify the wheat chromosomes involved in the translocations, and the results showed that A. cristatum 2P chromosome segments were translocated to the different wheat chromosomes, including 1A, 2A, 3A, 4A, 5A, 6A, 7A, 3B, 5B, 7B, 1D, 4D and 6D. Many different types of wheat-A. cristatum alien translocation lines would be valuable for not only identifying and cloning A. cristatum 2P-related genes and understanding the genetics and breeding effects of the translocation between A. cristatum chromosome 2P and wheat chromosomes, but also providing new germplasm resources for the wheat genetic improvement. PMID:26731742

Up-Regulation of Pro-Inflammatory Cytokines and Chemokine Production in Avian Influenza H9N2 Virus-Infected Human Lung Epithelial Cell Line (A549).

PubMed

Farzin, Hamidreza; Toroghi, Reza; Haghparast, Alireza

2016-01-01

Influenza H9N2 virus mostly infects avian species but poses a potential health risk to humans. Little is known about the mammalian host immune responses to H9N2 virus. To obtain insight into the innate immune responses of human lung epithelial cells to the avian H9N2 virus, the expressions of pro-inflammatory cytokines and chemokine in the human airway epithelial cells infected with avian H9N2 virus were examined by real-time quantitative reverse transcription polymerase chain reaction (qRT-PCR) and enzyme-linked immunosorbent assay (ELISA). H9N2 virus was able to cultivate in the human lung epithelial cell line (A549) and stimulate production of pro-inflammatory cytokines (IL-1β, IL-6) and chemokine (IL-8). Expressions of cytokine genes were up-regulated to a significantly higher level for IL-1β (p < 0.01), IL-6 (p < 0.01 after 12 hours and p < 0.05 after 24 hours) and IL-8 (p < 0.01 after 12 hours and p < 0.001 after 24 hours) in virus-cultured A549 cells as compared with non-virus-cultured cells. The amount of IL-6 and IL-1β proteins secreted into the culture medium was also increased after virus culture infection of A549 cell line compared to non-virus-cultured A549 cells and were significant in both IL-1β (p < 0.05 in 18 hours and p < 0.001 in 24-48 hours harvested supernatant) and IL-6 (p < 0.001). Silencing the p65 component of NF-κB in A549 cells suppressed the stimulatory effects of influenza virus on secretion of pro-inflammatory cytokines and chemokine. The findings in this study will broaden our understanding of host innate immune mechanisms and the pathogenesis of H9N2 influenza viruses in human respiratory epithelium.

A broadband permeability measurement of FeTaN lamination stack by the shorted microstrip line method

NASA Astrophysics Data System (ADS)

Chen, Xin; Ma, Yungui; Xu, Feng; Wang, Peng; Ong, C. K.

2009-01-01

In this paper, the microwave characteristics of a FeTaN lamination stack are studied with a shorted microstrip line method. The FeTaN lamination stack was fabricated by gluing 54 layers of FeTaN units with epoxy together. The FeTaN units were deposited on both sides of an 8 μm polyethylene terephthate (Mylar) film as the substrate by rf magnetron sputtering. On each side of the Mylar substrate, three 100-nm FeTaN layers are laminated with two 8 nm Al2O3 layers. The complex permeability of FeTaN lamination stack is calculated by the scattering parameters using the shorted load transmission line model based on the quasi-transverse-electromagnetic approximation. A full wave analysis combined with an optimization process is employed to determine the accurate effective permeability values. The optimized complex permeability data can be used for the microwave filter design.

Hydrodynamics of the Polyakov line in SU(N c) Yang-Mills

DOE PAGES

Liu, Yizhuang; Warchoł, Piotr; Zahed, Ismail

2015-12-08

We discuss a hydrodynamical description of the eigenvalues of the Polyakov line at large but finite N c for Yang-Mills theory in even and odd space-time dimensions. The hydro-static solutions for the eigenvalue densities are shown to interpolate between a uniform distribution in the confined phase and a localized distribution in the de-confined phase. The resulting critical temperatures are in overall agreement with those measured on the lattice over a broad range of N c, and are consistent with the string model results at N c = ∞. The stochastic relaxation of the eigenvalues of the Polyakov line out ofmore » equilibrium is captured by a hydrodynamical instanton. An estimate of the probability of formation of a Z(N c)bubble using a piece-wise sound wave is suggested.« less

The H+n-C5H12/n-C6H14→H2(v',j')+C5H11/C6H13 reactions: State-to-state dynamics and models of energy disposal

NASA Astrophysics Data System (ADS)

Picconatto, Carl A.; Srivastava, Abneesh; Valentini, James J.

2001-03-01

The rovibrational state distributions for the H2 product of the H+n-C5H12/n-C6H14→H2+C5H11/C6H13 reactions at 1.6 eV collision energy are reported. The results are compared to measurements made on the kinematically and energetically similar H+RH→H2+R (RH=CH4, C2H6, and C3H8) reactions as well as the atom-diatom reactions H+HX→H2+X(HX=HCl, HBr). For the title reactions, as for all the comparison reactions, the product appears in few of the energetically accessible states. This is interpreted as the result of a kinematic constraint on the product translational energy. Characteristic of the H+RH reactions we have previously studied, the title reactions show increasing rotational excitation of the H2 product with increasing vibrational excitation of it, a correlation that gets stronger as the size of the alkane increases. Trends and variations in the product energy disposal are analyzed and explained by a localized reaction model. This model predicates a truncation of the opacity function due to competing reactive sites in the polyatomic alkane reactant, and a relaxation of the otherwise tight coupling of energy and angular momentum conservation, because the polyatomic alkyl radical product is a sink for angular momentum.

Infrared spectra of CO2-doped hydrogen clusters, (H2)N-CO2.

PubMed

McKellar, A R W

2012-03-07

Clusters of para-H(2) and/or ortho-H(2) containing a single carbon dioxide molecule are studied by high resolution infrared spectroscopy in the 2300 cm(-1) region of the CO(2) ν(3) fundamental band. The (H(2))(N)-CO(2) clusters are formed in a pulsed supersonic jet expansion from a cooled nozzle and probed using a rapid scan tunable diode laser. Simple symmetric rotor type spectra are observed with little or no resolved K-structure, and prominent Q-branch features for ortho-H(2) but not para-H(2). Observed rotational constants and vibrational shifts are reported for ortho-H(2) up to N = 7 and para-H(2) up to N = 15, with the N > 7 assignments only made possible with the help of theoretical simulations. The para-H(2) cluster with N = 12 shows clear evidence for superfluid effects, in good agreement with theory. The presence of larger clusters with N > 15 is evident in the spectra, but specific assignments are not possible. Mixed para- + ortho-H(2) cluster transitions are well predicted by linear interpolation between corresponding pure cluster line positions. © 2012 American Institute of Physics

Absolute spectroscopy near 7.8 μm with a comb-locked extended-cavity quantum-cascade-laser.

PubMed

Lamperti, Marco; AlSaif, Bidoor; Gatti, Davide; Fermann, Martin; Laporta, Paolo; Farooq, Aamir; Marangoni, Marco

2018-01-22

We report for the first time the frequency locking of an extended-cavity quantum-cascade-laser (EC-QCL) to a near-infrared frequency comb. The locked laser source is exploited to carry out molecular spectroscopy around 7.8 μm with a line-centre frequency combined uncertainty of ~63 kHz. The strength of the approach, in view of an accurate retrieval of line centre frequencies over a spectral range as large as 100 cm -1 , is demonstrated on the P(40), P(18) and R(31) lines of the fundamental rovibrational band of N 2 O covering the centre and edges of the P and R branches. The spectrometer has the potential to be straightforwardly extended to other spectral ranges, till 12 μm, which is the current wavelength limit for commercial cw EC-QCLs.

Pinning in the flux-line-cutting regime of Bi 2Sr 2Ca 1Cu 2O 8 single crystals at high field

NASA Astrophysics Data System (ADS)

D'Anna, G.; André, M.-O.; Indenbom, M. V.; Benoit, W.

1994-09-01

Using a low-frequency torsion pendulum we show that in a Bi 2Sr 2Ca 1Cu 2O 8 single crystal the irreversibility line Birr( T) is frequency dependent down to 10 -5 Hz in the high-field regime. The activation energy has a logarithmic field dependence, U0( B)= U∗ 1n( B∗/ B). A microscopic model for flux-line-cutting and pancake collision yields quantitative expressions for U0 and for Birr( T)= B∗ exp(- T/T∗), which reproduce the experimental data very well.

Semi-empirical calculations of line-shape parameters and their temperature dependences for the ν6 band of CH3D perturbed by N2

NASA Astrophysics Data System (ADS)

Dudaryonok, A. S.; Lavrentieva, N. N.; Buldyreva, J.

2018-06-01

(J, K)-line broadening and shift coefficients with their temperature-dependence characteristics are computed for the perpendicular (ΔK = ±1) ν6 band of the 12CH3D-N2 system. The computations are based on a semi-empirical approach which consists in the use of analytical Anderson-type expressions multiplied by a few-parameter correction factor to account for various deviations from Anderson's theory approximations. A mathematically convenient form of the correction factor is chosen on the basis of experimental rotational dependencies of line widths, and its parameters are fitted on some experimental line widths at 296 K. To get the unknown CH3D polarizability in the excited vibrational state v6 for line-shift calculations, a parametric vibration-state-dependent expression is suggested, with two parameters adjusted on some room-temperature experimental values of line shifts. Having been validated by comparison with available in the literature experimental values for various sub-branches of the band, this approach is used to generate massive data of line-shape parameters for extended ranges of rotational quantum numbers (J up to 70 and K up to 20) typically requested for spectroscopic databases. To obtain the temperature-dependence characteristics of line widths and line shifts, computations are done for various temperatures in the range 200-400 K recommended for HITRAN and least-squares fit procedures are applied. For the case of line widths strong sub-branch dependence with increasing K is observed in the R- and P-branches; for the line shifts such dependence is stated for the Q-branch.

Production of N(+)-asterisk from N2 + hnu - Effective EUV emission yields from laboratory and dayglow data

NASA Technical Reports Server (NTRS)

Meier, R. R.; Samson, James A. R.; Chung, Y.; Lee, E.-M.; He, Z.-X.

1991-01-01

Photodissociative ionization of N2 into the unbound N2(+) H 2Sigma-g(+) state is identified as the parentage of a number of N(+) and N-excited states that contribute to the u.v. dayglow. Yields have been obtained for the production of extreme ultraviolet emission lines of N(+) and N from a laboratory experiment using a broadband synchrotron radiation source with fluorescence spectroscopy. The yields are termed 'effective', in that they are constant percentages of the H state cross section. These are compared wih effective yields needed to reproduce N II 1085 and 916 A lines from four dayglow observations using a model of solar energy deposition and photoelectron production and loss in the earth's thermosphere. The 1085 A effective yield measured in the laboratory (18 percent) agrees with that from the dayglow data (average of 17 percent) to well within experimental uncertainties. Thus, it is concluded that photodissociative ionization of N2 is the primary source of the N II 1085 A dayglow. However, there is an order of magnitude discrepancy among the various dayglow observations of the 1085/916 intensity ratio, only one of which is consistent with the laboratory observation of 4.4. Neither contamination by other dayglow features nor atmospheric extinction can account for the disparities. Laboratory measurements of N2 and O2 absorption cross sections at these wavelengths are also reported.

VizieR Online Data Catalog: ExoMol line lists for formaldehyde H2CO (Al-Refaie+,

NASA Astrophysics Data System (ADS)

Al-Refaie, A. F.; Yachmenev, A.; Tennyson, J.; Yurchenko, S. N.

2015-01-01

The data are in two parts. The first, h2co_0-70.dat contains a list of 10,296,998 rovibrational states. Each state is labelled with: 6 normal mode vibrational quantum numbers, and the vibrational symmetry; three rotational quantum numbers including the total angular momentum J, the projection of J in the z-axis K,rotational symmetry and the total symmetry quantum number Gamma In addition there are six local mode vibrational numbers and the largest coeffecient used to assign the state in question. Each rovibrational state has a unique number, which is the number of the row in which it appears in the file. This number is the means by which the state is related to the second part of the data system, the transitions files. The total degeneracy is also given to facilitate the intensity calculations. Because of their size, the transitions are listed in 100 separate files, each containing all the transitions in a 100cm-1 frequency range. These and their contents are ordered by increasing frequency. The name of the file includes the lowest frequency in the range; thus the a-00500.dat file contains all the transitions in the frequency range 500-600cm-1. The transition files contain three columns: the reference number in the energy file of the upper state; that of the lower state; and the Einstein A coefficient of the transition. The energy file and the transitions files are zipped, and need to be extracted before use. There is a Fortran 90 programme, s_AYTY.f90 which may be used to generate synthetic spectra (see s_AYTY.txt for details). Using this, it is possible to generate absorption or emission spectra in either 'stick' form or else cross-sections convoluted with a gaussian with the half-width at half maximum being specified by the user, or with a the temperature-dependent doppler half-width. Sample input files s*.inp for use with sSAlTY.f90 are supplied. (9 data files).

Foreign-gas broadening of nitrous oxide absorption lines.

NASA Technical Reports Server (NTRS)

Tubbs, L. D.; Williams, D.

1972-01-01

We have measured the foreign-gas broadening coefficients for collisional broadening of lines in the nu-3 fundamental of N2O by He, Ne, Ar, Kr, Xe, H2, D2, and CH4. These coefficients, which give the ratio of the line-broadening ability of these gases to the line-broadening ability of N2, can be used with recent measurements and calculations of N2 broadening to obtain optical collision cross sections.

Herschel observations of extraordinary sources: Analysis of the full Herschel/HIFI molecular line survey of sagittarius B2(N)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neill, Justin L.; Bergin, Edwin A.; Crockett, Nathan R.

2014-07-01

A sensitive broadband molecular line survey of the Sagittarius B2(N) star-forming region has been obtained with the Heterodyne Instrument for the Far-Infrared (HIFI) instrument on the Herschel Space Observatory, offering the first high spectral resolution look at this well-studied source in a wavelength region largely inaccessible from the ground (625-157 μm). From the roughly 8000 spectral features in the survey, a total of 72 isotopologues arising from 44 different molecules have been identified, ranging from light hydrides to complex organics, and arising from a variety of environments from cold and diffuse to hot and dense gas. We present a localmore » thermodynamic equilibrium (LTE) model to the spectral signatures of each molecule, constraining the source sizes for hot core species with complementary Submillimeter Array interferometric observations and assuming that molecules with related functional group composition are cospatial. For each molecule, a single model is given to fit all of the emission and absorption features of that species across the entire 480-1910 GHz spectral range, accounting for multiple temperature and velocity components when needed to describe the spectrum. As with other HIFI surveys toward massive star-forming regions, methanol is found to contribute more integrated line intensity to the spectrum than any other species. We discuss the molecular abundances derived for the hot core where the LTE approximation is generally found to describe the spectrum well, in comparison to abundances derived for the same molecules in the Orion KL region from a similar HIFI survey. Notably, we find significantly higher abundances of amine- and amide-bearing molecules (CH{sub 3}NH{sub 2}, CH{sub 2}NH, and NH{sub 2}CHO) toward Sgr B2(N) than Orion KL and lower abundances of some complex oxygen-bearing molecules (CH{sub 3}OCHO in particular). In addition to information on the chemical composition of the hot core, the strong far-infrared dust continuum

First Measurement of the 14N/15N Ratio in the Analog of the Sun Progenitor OMC-2 FIR4

NASA Astrophysics Data System (ADS)

Kahane, Claudine; Jaber Al-Edhari, Ali; Ceccarelli, Cecilia; López-Sepulcre, Ana; Fontani, Francesco; Kama, Mihkel

2018-01-01

We present a complete census of the 14N/15N isotopic ratio in the most abundant N-bearing molecules toward the cold envelope of the protocluster OMC-2 FIR4, the best known Sun progenitor. To this scope, we analyzed the unbiased spectral survey obtained with the IRAM 30 m telescope at 3, 2, and 1 mm. We detected several lines of CN, HCN, HNC, HC3N, N2H+, and their respective 13C and 15N isotopologues. The lines’ relative fluxes are compatible with LTE conditions, and moderate line opacities have been corrected via a population diagram method or theoretical relative intensity ratios of the hyperfine structures. The five species lead to very similar 14N/15N isotopic ratios, without any systematic difference between amine- and nitrile-bearing species as previously found in other protostellar sources. The weighted average of the 14N/15N isotopic ratio is 270 ± 30. This 14N/15N value is remarkably consistent with the [250–350] range measured for the local galactic ratio but significantly differs from the ratio measured in comets (around 140). High-angular resolution observations are needed to examine whether this discrepancy is maintained at smaller scales. In addition, using the CN, HCN, and HC3N lines, we derived a 12C/13C isotopic ratio of 50 ± 5.

Characterizing Neutron Diagnostics on the nTOF Line at SUNY Geneseo

NASA Astrophysics Data System (ADS)

Harrison, Hannah; Seppala, Hannah; Visca, Hannah; Wakwella, Praveen; Fletcher, Kurt; Padalino, Stephen; Forrest, Chad; Regan, Sean; Sangster, Craig

2016-10-01

Charged particle beams from SUNY Geneseo's 1.7 MV Tandem Pelletron Accelerator induce nuclear reactions that emit neutrons ranging from 0.5 to 17.9 MeV via 2H(d,n)3He and 11B(d,n)12C. This adjustable neutron source can be used to calibrate ICF and HEDP neutron scintillators for ICF diagnostics. However, gamma rays and muons, which are often present during an accelerator-based calibration, are difficult to differentiate from neutron signals in scintillators. To mitigate this problem, a new neutron time-of-flight (nTOF) line has been constructed. The nTOF timing is measured using the associated particle technique. A charged particle produced by the nuclear reaction serves as a start signal, while its associated neutron is the stop signal. Each reaction is analyzed event-by-event to determine whether the scintillator signal was generated by a neutron, gamma or muon. Using this nTOF technique, the neutron response for different scintillation detectors can be determined. Funded in part by a LLE contract through the DOE.

Towards completing the cyclopropenylidene cycle: rovibrational analysis of cyclic N3+, CNN, HCNN+, and CNC.

PubMed

Fortenberry, Ryan C; Lee, Timothy J; Huang, Xinchuan

2017-08-30

The simple aromatic hydrocarbon, cyclopropenylidene (c-C 3 H 2 ), is a known, naturally-occurring molecule. The question remains as to whether its isoelectronic, cyclic, fellow aromatics of c-N 3 + , c-CNN, HCNN + , and c-CNC - are as well. Each of these are exciting objects for observation of Titan, and the rotational constants and vibrational frequencies produced here will allow for remote sensing of Titan's atmosphere or other astrophysical or terrestrial sources. None of these four aromatic species are vibrationally strong absorbers/emitters, but the two ions, HCNN + and c-CNC - , have dipole moments of greater than 3 D and 1 D, respectively, making them good targets for rotational spectroscopic observation. Each of these molecules is shown here to exhibit its own, unique vibrational properties, but the general trends put the vibrational behavior for corresponding fundamental modes within close ranges of one another, even producing nearly the same heavy atom, symmetric stretching frequencies for HCNN + and c-C 3 H 2 at 1600 cm -1 . The c-N 3 + cation is confirmed to be fairly unstable and has almost no intensity in its ν 2 fundamental. Hence, it will likely remain difficult to characterize experimentally.

Everolimus plus exemestane as first-line therapy in HR⁺, HER2⁻ advanced breast cancer in BOLERO-2.

PubMed

Beck, J Thaddeus; Hortobagyi, Gabriel N; Campone, Mario; Lebrun, Fabienne; Deleu, Ines; Rugo, Hope S; Pistilli, Barbara; Masuda, Norikazu; Hart, Lowell; Melichar, Bohuslav; Dakhil, Shaker; Geberth, Matthias; Nunzi, Martina; Heng, Daniel Y C; Brechenmacher, Thomas; El-Hashimy, Mona; Douma, Shyanne; Ringeisen, Francois; Piccart, Martine

2014-02-01

The present exploratory analysis examined the efficacy, safety, and quality-of-life effects of everolimus (EVE) + exemestane (EXE) in the subgroup of patients in BOLERO-2 whose last treatment before study entry was in the (neo)adjuvant setting. In BOLERO-2, patients with hormone-receptor-positive (HR(+)), human epidermal growth factor receptor-2-negative (HER2(-)) advanced breast cancer recurring/progressing after a nonsteroidal aromatase inhibitor (NSAI) were randomly assigned (2:1) to receive EVE (10 mg/day) + EXE (25 mg/day) or placebo (PBO) + EXE. The primary endpoint was progression-free survival (PFS) by local assessment. Overall, 137 patients received first-line EVE + EXE (n = 100) or PBO + EXE (n = 37). Median PFS by local investigator assessment nearly tripled to 11.5 months with EVE + EXE from 4.1 months with PBO + EXE (hazard ratio = 0.39; 95 % CI 0.25-0.62), while maintaining quality of life. This was confirmed by central assessment (15.2 vs 4.2 months; hazard ratio = 0.32; 95 % CI 0.18-0.57). The marked PFS improvement in patients receiving EVE + EXE as first-line therapy for disease recurrence during or after (neo)adjuvant NSAI therapy supports the efficacy of this combination in the first-line setting. Furthermore, the results highlight the potential benefit of early introduction of EVE + EXE in the management of HR(+), HER2(-) advanced breast cancer in postmenopausal patients.

Episome-generated N-myc antisense RNA restricts the differentiation potential of primitive neuroectodermal cell lines.

PubMed Central

Whitesell, L; Rosolen, A; Neckers, L M

1991-01-01

Neuroectodermal tumors of childhood provide a unique opportunity to examine the role of genes potentially regulating neuronal growth and differentiation because many cell lines derived from these tumors are composed of at least two distinct morphologic cell types. These types display variant phenotypic characteristics and spontaneously interconvert, or transdifferentiate, in vitro. The factors that regulate transdifferentiation are unknown. Application of antisense approaches to the transdifferentiation process has allowed us to explore the precise role that N-myc may play in regulating developing systems. We now report construction of an episomally replicating expression vector designed to generate RNA antisense to part of the human N-myc gene. Such a vector is able to specifically inhibit N-myc expression in cell lines carrying both normal and amplified N-myc alleles. Inhibition of N-myc expression blocks transdifferentiation in these lines, with accumulation of cells of an intermediate phenotype. A concomitant decrease in growth rate but not loss of tumorigenicity was observed in the N-myc nonamplified cell line CHP-100. Vector-generated antisense RNA should allow identification of genes specifically regulated by the proto-oncogene N-myc. Images PMID:1996098

AC Glow Discharge Plasma in N2O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yousif, F. B.; Martinez, H.; Robledo-Martinez, A.

2006-12-04

This paper considers the optical and electrical characterization of AC glow discharge plasma in the abnormal glow mode used for optical emission spectroscopy. The total discharge current and applied voltage are measured using conventional techniques. The electrical characteristics of the planer-cathode glow discharge confirmed that the plasma is operating at abnormal discharge mode characterized by the increases in the operating voltage as the current was raised under given pressure. Optical emission spectroscopy was used to determine the main emission lines of the glow discharge plasma of N2O at pressures between 0.5 and 4.0 Torr. It shows that the discharge emissionmore » range is mainly within 300-400 nm. The emission lines correspond to NO, O2, and O{sub 2}{sup +} are the dominant lines in the glow discharge plasma in the present study. Intensity of the emission lines show linear increase with the discharge current up to 0.4 A followed by saturation at higher currents. No emission lines were observed in this work corresponding to atomic oxygen or nitrogen.« less

Unveiling the chemistry of interstellar CH. Spectroscopy of the 2 THz N = 2 ← 1 ground state line

NASA Astrophysics Data System (ADS)

Wiesemeyer, H.; Güsten, R.; Menten, K. M.; Durán, C. A.; Csengeri, T.; Jacob, A. M.; Simon, R.; Stutzki, J.; Wyrowski, F.

2018-04-01

Context. The methylidyne radical CH is commonly used as a proxy for molecular hydrogen in the cold, neutral phase of the interstellar medium. The optical spectroscopy of CH is limited by interstellar extinction, whereas far-infrared observations provide an integral view through the Galaxy. While the HF ground state absorption, another H2 proxy in diffuse gas, frequently suffers from saturation, CH remains transparent both in spiral-arm crossings and high-mass star forming regions, turning this light hydride into a universal surrogate for H2. However, in slow shocks and in regions dissipating turbulence its abundance is expected to be enhanced by an endothermic production path, and the idea of a "canonical" CH abundance needs to be addressed. Aim. The N = 2 ← 1 ground state transition of CH at λ149 μm has become accessible to high-resolution spectroscopy thanks to the German Receiver for Astronomy at Terahertz Frequencies (GREAT) aboard the Stratospheric Observatory for Infrared Astronomy (SOFIA). Its unsaturated absorption and the absence of emission from the star forming regions makes it an ideal candidate for the determination of column densities with a minimum of assumptions. Here we present an analysis of four sightlines towards distant Galactic star forming regions, whose hot cores emit a strong far-infrared dust continuum serving as background signal. Moreover, if combined with the sub-millimeter line of CH at λ560 μm , environments forming massive stars can be analyzed. For this we present a case study on the "proto-Trapezium" cluster W3 IRS5. Methods: While we confirm the global correlation between the column densities of HF and those of CH, both in arm and interarm regions, clear signposts of an over-abundance of CH are observed towards lower densities. However, a significant correlation between the column densities of CH and HF remains. A characterization of the hot cores in the W3 IRS5 proto-cluster and its envelope demonstrates that the sub

Measurement of 235U(n,n'γ) and 235U(n,2nγ) reaction cross sections

NASA Astrophysics Data System (ADS)

Kerveno, M.; Thiry, J. C.; Bacquias, A.; Borcea, C.; Dessagne, P.; Drohé, J. C.; Goriely, S.; Hilaire, S.; Jericha, E.; Karam, H.; Negret, A.; Pavlik, A.; Plompen, A. J. M.; Romain, P.; Rouki, C.; Rudolf, G.; Stanoiu, M.

2013-02-01

The design of generation IV nuclear reactors and the studies of new fuel cycles require knowledge of the cross sections of various nuclear reactions. Our research is focused on (n,xnγ) reactions occurring in these new reactors. The aim is to measure unknown cross sections and to reduce the uncertainty on present data for reactions and isotopes of interest for transmutation or advanced reactors. The present work studies the 235U(n,n'γ) and 235U(n,2nγ) reactions in the fast neutron energy domain (up to 20 MeV). The experiments were performed with the Geel electron linear accelerator GELINA, which delivers a pulsed white neutron beam. The time characteristics enable measuring neutron energies with the time-of-flight (TOF) technique. The neutron induced reactions [in this case inelastic scattering and (n,2n) reactions] are identified by on-line prompt γ spectroscopy with an experimental setup including four high-purity germanium (HPGe) detectors. A fission ionization chamber is used to monitor the incident neutron flux. The experimental setup and analysis methods are presented and the model calculations performed with the TALYS-1.2 code are discussed.

Theoretical Stark broadening parameters for spectral lines arising from the 2p5ns, 2p5np and 2p5nd electronic configurations of Mg III

NASA Astrophysics Data System (ADS)

Colón, C.; Moreno-Díaz, C.; Alonso-Medina, A.

2013-10-01

In the present work we report theoretical Stark widths and shifts calculated using the Griem semi-empirical approach, corresponding to 237 spectral lines of Mg III. Data are presented for an electron density of 1017 cm-3 and temperatures T = 0.5-10.0 (104K). The matrix elements used in these calculations have been determined from 23 configurations of Mg III: 2s22p6, 2s22p53p, 2s22p54p, 2s22p54f and 2s22p55f for even parity and 2s22p5ns (n = 3-6), 2s22p5nd (n = 3-9), 2s22p55g and 2s2p6np (n = 3-8) for odd parity. For the intermediate coupling (IC) calculations, we use the standard method of least-squares fitting from experimental energy levels by means of the Cowan computer code. Also, in order to test the matrix elements used in our calculations, we present calculated values of 70 transition probabilities of Mg III spectral lines and 14 calculated values of radiative lifetimes of Mg III levels. There is good agreement between our calculations and experimental radiative lifetimes. Spectral lines of Mg III are relevant in astrophysics and also play an important role in the spectral analysis of laboratory plasma. Theoretical trends of the Stark broadening parameter versus the temperature for relevant lines are presented. No values of Stark parameters can be found in the bibliography.

Structure and NMR spectra of some [2.2]paracyclophanes. The dilemma of [2.2]paracyclophane symmetry.

PubMed

Dodziuk, Helena; Szymański, Sławomir; Jaźwiński, Jarosław; Ostrowski, Maciej; Demissie, Taye Beyene; Ruud, Kenneth; Kuś, Piotr; Hopf, Henning; Lin, Shaw-Tao

2011-09-29

Density functional theory (DFT) quantum chemical calculations of the structure and NMR parameters for highly strained hydrocarbon [2.2]paracyclophane 1 and its three derivatives are presented. The calculated NMR parameters are compared with the experimental ones. By least-squares fitting of the (1)H spectra, almost all J(HH) coupling constants could be obtained with high accuracy. Theoretical vicinal J(HH) couplings in the aliphatic bridges, calculated using different basis sets (6-311G(d,p), and Huz-IV) reproduce the experimental values with essentially the same root-mean-square (rms) error of about 1.3 Hz, regardless of the basis set used. These discrepancies could be in part due to a considerable impact of rovibrational effects on the observed J(HH) couplings, since the latter show a measurable dependence on temperature. Because of the lasting literature controversies concerning the symmetry of parent compound 1, D(2h) versus D(2), a critical analysis of the relevant literature data is carried out. The symmetry issue is prone to confusion because, according to some literature claims, the two hypothetical enantiomeric D(2) structures of 1 could be separated by a very low energy barrier that would explain the occurrence of rovibrational effects on the observed vicinal J(HH) couplings. However, the D(2h) symmetry of 1 with a flat energy minimum could also account for these effects.

High resolution study of strongly interacting ν3(F2)/ν1(A1) bands of MSiH4 (M = 28 , 29 , 30)

NASA Astrophysics Data System (ADS)

Ulenikov, O. N.; Gromova, O. V.; Bekhtereva, E. S.; Raspopova, N. I.; Fomchenko, A. L.; Sydow, C.; Bauerecker, S.

2017-11-01

The high resolution (0.0021-0.0025 cm-1) infrared spectra of SiH4 in natural abundance (92.23 % of 28SiH4, 4.68 % of 29SiH4, and 3.09 % of 30SiH4) were measured in the 2000-2350 cm-1 region with a Bruker IFS 120HR Fourier transform spectrometer. The 2584 transitions with Jmax. = 27 were assigned to the ν3 and ν1 bands of 28SiH4. Rotational, centrifugal distortion, tetrahedral splitting, and resonance interaction parameters for the (0010) and (1000) vibrational states were determined from the weighted fit of experimental line positions. The obtained set of parameters reproduces the initial experimental data with an accuracy close to experimental uncertainties. The results of analogous analyses of the 29SiH4 and 30SiH4 isotopologues (the numbers of assigned transitions are 811 and 986 both with Jmax. = 23) were made with the use of the isotopic substitution theory relations. A further analysis of 379 experimental ro-vibrational lines of the ν3 and ν1 bands of 28SiH4 was performed using the Hartmann-Tran profile to simulate the measured line shape and to determine experimental line intensities. The 4 effective dipole moment parameters were obtained on that basis from the weighted fit, which reproduce the initial experimental intensities of the 379 initial lines (both strong and weak) with the drms = 7.6 % (the 148 strongest lines are reproduced with the drms = 5.0 %). Analogous analyses were made for the two other isotopic species, 29SiH4, and 30SiH4. A detailed line list of transitions in the region of 2000-2350 cm-1 is presented. The half-widths of 100 ro-vibrational lines (Jup.max. = 17) are analyzed from the multi-spectrum fit, and self-pressure broadening coefficients are determined.

Investigation of the Semicoa 2N7616 and 2N7425 and the Microsemi 2N7480 for Single-Event Gate Rupture and Single-Event Burnout

NASA Technical Reports Server (NTRS)

Scheick, Leif

2014-01-01

Single-event-effect test results for hi-rel total-dose-hardened power MOSFETs are presented in this report. The 2N7616 and the 2N7425 from Semicoa and the 2N7480 from International Rectifier were tested to NASA test condition standards and requirements. The 2N7480 performed well and the data agree with the manufacture's data. The 2N7616 and 2N7425 were entry parts from Semicoa using a new device architecture. Unfortunately, the device performed poorly and Semicoa is withdrawing power MOSFETs from it line due to these data. Vertical metal-oxide-semiconductor field-effect transistors (MOSFETs) are the most commonly used power transistor. MOSFETs are typically employed in power supplies and high current switching applications. Due to the inherent high electric fields in the device, power MOSFETs are sensitive to heavy ion irradiation and can fail catastrophically as a result of single-event gate rupture (SEGR) or single-event burnout (SEB). Manufacturers have designed radiation-hardened power MOSFETs for space applications. See [1] through [5] for more information. The objective of this effort was to investigate the SEGR and SEB responses of two power MOSFETs recently produced. These tests will serve as a limited verification of these parts. It is acknowledged that further testing on the respective parts may be needed for some mission profiles.

Preparation of Vibrationally Excited H2 in a Coherent Superposition of M-States Using Stark Induced Adiabatic Raman Passage (SARP)

NASA Astrophysics Data System (ADS)

Mukherjee, Nandini; Dong, Wenrui; Perreault, William; Zare, Richard

2017-04-01

We prepare a large ensemble of rovibrationally excited (v = 1, J = 2) H2 molecules in a coherent superposition of M-states using Stark-induced adiabatic Raman passage (SARP) with linearly polarized single mode pump (532 nm) and Stokes (699 nm) laser pulses of duration 6 ns and 4 ns. A biaxial superposition state, | ψ〉 = 1/ √2 [ | v = 1, J = 2, M = -2〉- | v = 1, J = 2, M = + 2〉], is prepared using SARP with a sequence of a pump laser pulse partially overlapping with a cross polarized Stokes laser pulse co-propagating along the quantization z-axis. The degree of phase coherence is measured by recording interference fringes in the ion signal produced using the O(2) line of 2 +1 resonance enhanced multiphoton ionization (REMPI) from the rovibrationally excited (v = 1, J = 2) level as a function of REMPI laser polarization angle. The ion signal is measured using a time-of-flight mass spectrometer. Nearly 60% population transfer from H2 (v = 0, J = 0) ground state to the superposition state in H2 (v = 1, J = 2) is measured from the depletion of Q(0) REMPI signal of the (v = 0, J = 0) ground state. The M-state superposition behaves much like a multi-slit interferometer where the number of slits, i.e. the number of M-states, and their separations, i.e. the relative phase, can be varied experimentally. This work has been supported by the U.S. Army Research Office.

Waste Conversion into n-Caprylate and n-Caproate: Resource Recovery from Wine Lees Using Anaerobic Reactor Microbiomes and In-line Extraction

PubMed Central

Kucek, Leo A.; Xu, Jiajie; Nguyen, Mytien; Angenent, Largus T.

2016-01-01

To convert wastes into sustainable liquid fuels and chemicals, new resource recovery technologies are required. Chain elongation is a carboxylate-platform bioprocess that converts short-chain carboxylates (SCCs) (e.g., acetate [C2] and n-butyrate [C4]) into medium-chain carboxylates (MCCs) (e.g., n-caprylate [C8] and n-caproate [C6]) with hydrogen gas as a side product. Ethanol or another electron donor (e.g., lactate, carbohydrate) is required. Competitive MCC productivities, yields (product vs. substrate fed), and specificities (product vs. all products) were only achieved previously from an organic waste material when exogenous ethanol had been added. Here, we converted a real organic waste, which inherently contains ethanol, into MCCs with n-caprylate as the target product. We used wine lees, which consisted primarily of settled yeast cells and ethanol from wine fermentation, and produced MCCs with a reactor microbiome. We operated the bioreactor at a pH of 5.2 and with continuous in-line extraction and achieved a MCC productivity of 3.9 g COD/L-d at an organic loading rate of 5.8 g COD/L-d, resulting in a promising MCC yield of 67% and specificities of 36% for each n-caprylate and n-caproate (72% for both). Compared to all other studies that used complex organic substrates, we achieved the highest n-caprylate-to-ncaproate product ratio of 1.0 (COD basis), because we used increased broth-recycle rates through the forward membrane contactor, which improved in-line extraction rates. Increased recycle rates also allowed us to achieve the highest reported MCC production flux per membrane surface area thus far (20.1 g COD/m2-d). Through microbial community analyses, we determined that an operational taxonomic unit (OTU) for Bacteroides spp. was dominant and was positively correlated with increased MCC productivities. Our data also suggested that the microbiome may have been shaped for improved MCC production by the high broth-recycle rates. Comparable abiotic

HIFI Spectroscopy of H2O Submillimeter Lines in Nuclei of Actively Star-forming Galaxies

NASA Astrophysics Data System (ADS)

Liu, L.; Weiß, A.; Perez-Beaupuits, J. P.; Güsten, R.; Liu, D.; Gao, Y.; Menten, K. M.; van der Werf, P.; Israel, F. P.; Harris, A.; Martin-Pintado, J.; Requena-Torres, M. A.; Stutzki, J.

2017-09-01

We present a systematic survey of multiple velocity-resolved H2O spectra using Herschel/Heterodyne Instrument for the Far Infrared (HIFI) toward nine nearby actively star-forming galaxies. The ground-state and low-excitation lines (E up ≤ 130 K) show profiles with emission and absorption blended together, while absorption-free medium-excitation lines (130 K ≤ E up ≤ 350 K) typically display line shapes similar to CO. We analyze the HIFI observation together with archival SPIRE/PACS H2O data using a state-of-the-art 3D radiative transfer code that includes the interaction between continuum and line emission. The water excitation models are combined with information on the dust and CO spectral line energy distribution to determine the physical structure of the interstellar medium (ISM). We identify two ISM components that are common to all galaxies: a warm ({T}{dust}˜ 40{--}70 K), dense (n({{H}})˜ {10}5{--}{10}6 {{cm}}-3) phase that dominates the emission of medium-excitation H2O lines. This gas phase also dominates the far-IR emission and the CO intensities for {J}{up}> 8. In addition, a cold ({T}{dust}˜ 20{--}30 K), dense (n({{H}})˜ {10}4{--}{10}5 {{cm}}-3), more extended phase is present. It outputs the emission in the low-excitation H2O lines and typically also produces the prominent line absorption features. For the two ULIRGs in our sample (Arp 220 and Mrk 231) an even hotter and more compact (R s ≤ 100 pc) region is present, which is possibly linked to AGN activity. We find that collisions dominate the water excitation in the cold gas and for lines with {E}{up}≤slant 300 K and {E}{up}≤slant 800 K in the warm and hot component, respectively. Higher-energy levels are mainly excited by IR pumping.

VizieR Online Data Catalog: ExoMol line lists for H216O2 (Al-Refaie+, 2016)

NASA Astrophysics Data System (ADS)

Al-Refaie, A. F.; Polyansky, O. L.; Tennyson, J.; Yurchenko, S. N.

2016-06-01

The data are in two parts. The first, h2o20-85.dat contains a list of 7,560,352 rovibrational states. Each state is labelled with: six normal mode vibrational quantum numbers the torsional symmetry number (tau) and the vibrational symmetry; three rotational quantum numbers including the total angular momentum J and rotational symmetry; the total symmetry quantum number Gamma and the running number in the same J,Gamma block. In addition there are six local mode vibrational numbers and the largest coefficient used to assign the state in question. Each rovibrational state has a unique number, which is the number of the row in which it appears in the file. This number is the means by which the state is related to the second part of the data system, the transitions files. The total degeneracy is also given to facilitate the intensity calculations. Because of their size, the transitions are listed in 60 separate files, each containing all the transitions in a 100cm-1 frequency range. These and their contents are ordered by increasing frequency. The name of the file includes the lowest frequency in the range; thus the a-0500.dat file contains all the transitions in the frequency range 500-600cm-1. The transition files contain three columns: the reference number in the energy file of the upper state; that of the lower state; and the Einstein A coefficient of the transition. The energy file and the transitions files are zipped, and need to be extracted before use. There is a Fortran 90 programme, s_APTY.f90 which may be used to generate synthetic spectra (see s_APTY.txt for details). Using this, it is possible to generate absorption or emission spectra in either 'stick' form or else cross-sections convoluted with a gaussian with the half-width at half maximum being specified by the user, or with a the temperature-dependent doppler half-width. Sample input files s*.inp for use with sAPTY.f90 are supplied. (10 data files).

Determination of the intracellular Ca2+ concentration in the N1E-115 neuronal cell line in perspective of its use for peripheric nerve regeneration.

PubMed

Rodrigues, J M; Luís, A L; Lobato, J V; Pinto, M V; Lopes, M A; Freitas, M; Geuna, S; Santos, J D; Maurício, A C

2005-01-01

Entubulation repair of peripheral nerve injuries has a lengthy history. Several experimental and clinical studies have explored the effectiveness of many biodegradable and non-degradable tubes with or without addition of molecules and cells. The main objective of the present study was to develop an economical and also an easy way for culturing a neural cell line which was capable of growing, differentiating and producing locally nerve growth factors that are otherwise extremely expensive, inside 90 PLA/10 PLG nerve guides. For this purpose the authors have chosen the N1E-115 cell line, a clone of cells derived from mouse neuroblastoma C-1300 with the perspective of using this differentiated cellular system to cover the inside of 90 PLA/10 PLG nerve guides placed to bridge a gap in the rat sciatic nerve experimental model. The N1E-115 cells proliferate in normal culture medium but undergo neuronal differentiation in response to DMSO. Upon induction of differentiation, proliferation of N1E-115 cells ceases, extensive neurite outgrowth is observed and the membranes become highly excitable. While it is known that Ca2+ serves as an important intracellular signal for various cellular processes, such as growth and differentiation. It is also known that can be toxic to cells and is involved in the triggering of events leading to excitotoxic cell death in neurons. The [Ca2+]i in non-differentiated N1E-115 cells and after distinct periods of differentiation, have been determined by the epifluorescence technique using the Fura-2-AM probe. The results of this quantitative assessment revealed that N1E-115 cells which undergo neuronal differentiation for 48 hours in the presence of 1.5% DMSO are best qualified to be used to cover the interior of the nerve guides since the [Ca2+]i was not found to be elevated indicating thus that the onset the cell death processes was not occurred.

First analysis of the hybrid A/B-type 2ν8 band of C2HD3 and the Coriolis interactions with the ν3 + ν4 band by high-resolution FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Ng, L. L.; Tan, T. L.; Chia, A. H.

2018-02-01

Using a Fourier transform infrared (FTIR) spectrometer, the spectrum of the 2ν8 band of ethylene-d3 (C2HD3) was measured between 1745 to 1905 cm-1 at an unapodized resolution of 0.0063 cm-1. For the first time, 1664 perturbed and unperturbed a- and b-type absorption lines of the band were recorded, assigned and fitted using the Watson's A-reduced Hamiltonian in the Ir representation to derive rovibrational constants up to four quartic terms for the v8 = 2 state. Three rotational constants of the v3 = v4 = 1 state were also derived for the first time in this work from the analysis of the a- and b-Coriolis resonances with the v8 = 2 state, together with a set of resonance parameters. The root-mean-square (rms) deviation of the FTIR fit was 0.0010 cm-1. The band centers of the 2ν8 and ν3 + ν4 bands were determined to be 1831.457508 ± 0.000071 cm-1 and 1812.629 ± 0.022 cm-1, respectively. A set of ground state rovibrational constants of C2HD3 up to five quartic constants was also derived with improved precision from a simultaneous fit of 377 ground state combination differences (GSCDs) from a-type infrared transitions of the present analysis and 906 GSCDs from the previous work on the C-type ν8 band, with an rms deviation of 0.00043 cm-1. The transition dipole moment ratio | μa/μb | was found to be 2.194 ± 0.072.

The 51.8 micron (0 3) line emission observed in four galactic H 2 regions

NASA Technical Reports Server (NTRS)

Melnick, G.; Gull, G. E.; Harwit, M.

1978-01-01

The (0 III) 51.8 microns line from four H II regions, M42, M17, W51 and NGC 6375A was detected. Respective line strengths are 7 x 10 to the minus 15 power, 1.0 x 10 to the minus 14 power, 2.1 x 10 to the minus 15 power and 2.6 x 10 to the minus 15 power watt cm/2. Observations are consistent with previously reported line position and place the line at 51.80 + or 0.05 micron. When combined with the 88.35 microns (0 III) reported earlier, clumping seems to be an important factor in NGC 6375A and M42 and to a lesser extent in W51 and M17. The combined data also suggest an (0 III) abundance of approximately 3 x 0.0001 sub n e' a factor of 2 greater than previously assumed.

N-H stretching vibrations of guanosine-cytidine base pairs in solution: ultrafast dynamics, couplings, and line shapes.

PubMed

Fidder, Henk; Yang, Ming; Nibbering, Erik T J; Elsaesser, Thomas; Röttger, Katharina; Temps, Friedrich

2013-02-07

Dynamics and couplings of N-H stretching vibrations of chemically modified guanosine-cytidine (G·C) base pairs in chloroform are investigated with linear infrared spectroscopy and ultrafast two-dimensional infrared (2D-IR) spectroscopy. Comparison of G·C absorption spectra before and after H/D exchange reveals significant N-H stretching absorption in the region from 2500 up to 3300 cm(-1). Both of the local stretching modes ν(C)(NH(2))(b) of the hydrogen-bonded N-H moiety of the cytidine NH(2) group and ν(G)(NH) of the guanosine N-H group contribute to this broad absorption band. Its complex line shape is attributed to Fermi resonances of the N-H stretching modes with combination and overtones of fingerprint vibrations and anharmonic couplings to low-frequency modes. Cross-peaks in the nonlinear 2D spectra between the 3491 cm(-1) free N-H oscillator band and the bands centered at 3145 and 3303 cm(-1) imply N-H···O═C hydrogen bond character for both of these transitions. Time evolution illustrates that the 3303 cm(-1) band is composed of a nearly homogeneous band absorbing at 3301 cm(-1), ascribed to ν(G)(NH(2))(b), and a broad inhomogeneous band peaking at 3380 cm(-1) with mainly guanosine carbonyl overtone character. Kinetics and signal strengths indicate a <0.2 ps virtually complete population transfer from the excited ν(G)(NH(2))(b) mode to the ν(G)(NH) mode at 3145 cm(-1), suggesting lifetime broadening as the dominant source for the homogeneous line shape of the 3301 cm(-1) transition. For the 3145 cm(-1) band, a 0.3 ps population lifetime was obtained.

VizieR Online Data Catalog: A variationally computed hot NH3 line list - BYTe (Yurchenko+, 2011)

NASA Astrophysics Data System (ADS)

Yurchenko, S. N.; Barber, R. J.; Tennyson, J.

2010-11-01

We present 'BYTe' a comprehensive 'hot' line list of ro-vibrational transitions of ammonia, 14NH3, in its ground electronic state. It comprises 1,138,323,351 transitions with frequencies up to 12,000cm-1^, constructed from 1,373,897 energy levels below 18,000cm-1^ having J values less than 37. The line list is sufficiently accurate and complete for high resolution spectroscopy and atmospheric modelling of astrophysical objects, including brown dwarfs and exoplanets at temperatures up to 1,500K. The data are in two parts. The first, nh3_0-41.dat contains a list of 4,167,360 rovibrational states, ordered by J (max= 41), symmetry block and energy (in cm-1^). Only one third of the states (1,373,897) are within the parameters used for generating transitions (see above), but all the states are required for computing temperature-dependent partition functions. Each state is labelled with: seven normal mode vibrational quantum numbers; three rotational quantum numbers and the total symmetry quantum number, Gamma. In addition there are six local mode vibrational numbers and a local mode vibrational symmetry quantum numbers, which we include because the basis set used in our calculations is expressed in terms of these local mode quantum numbers. Each rovibrational state has a unique number, which is the number of the row in which it appears in the file. This number is the means by which the state is related to the second part of the data system, the transitions files. Because of their size, the transitions are listed in 120 separate files, each containing all the transitions in a 100cm-1^ frequency range. These and their contents are ordered by increasing frequency. The name of the file includes the lowest frequency in the range; thus the a-00500.dat file contains all the transitions in the frequency range 500-600cm-1^. The transition files contain three columns: the reference number in the energy file of the upper state; that of the lower state; and the Einstein A

High-resolution far-infrared synchrotron FTIR spectrum of the ν12 band of formamide-d1 (DCONH2)

NASA Astrophysics Data System (ADS)

Tan, T. L.; Wu, Q. Y.; Ng, L. L.; Appadoo, Dominique R. T.; McNaughton, Don

2018-05-01

The spectrum of the ν12 band of formamide-d1 (DCONH2) was recorded using a synchrotron Fourier transform infrared (FTIR) spectrometer coupled to the Australian Synchrotron THz/Far-IR beamline, with an unapodized resolution of 0.00096 cm-1 in the 350-210 cm-1 region. For the first time, rovibrational constants up to five quartic and two sextic terms were derived for the v12 = 1 state through the fitting of a total of 2072 far-infrared transitions using Watson's A-reduced Hamiltonian in the Ir representation with a root-mean-square (rms) deviation of 0.000073 cm-1. The band centre of the ν12 band of DCONH2 was found to be 289.3327553(47) cm-1 although the experimental uncertainty was limited to ±0.0002 cm-1. Ground state rovibrational constants of DCONH2 up to five quartic and two sextic constants were derived from a fit of 847 ground state combination differences (GSCDs) obtained from the infrared transitions of the ν12 band, together with 6 previously reported microwave transitions, with a rms deviation of 0.000108 cm-1. The ground state rotational constants (A, B, and C) of DCONH2 were improved while the ground state centrifugal distortion constants were accurately obtained for the first time. The uncertainty of the measured infrared lines was estimated to be ±0.0002 cm-1. From the ground state rotational constants, the inertial defect of DCONH2 was calculated to be 0.0169412(11) uÅ2.

Analysis of the Fourier Spectrum of the ν2 Inversion Band of the 15NHD2 Molecule

NASA Astrophysics Data System (ADS)

Fomchenko, A. L.; Belova, A. S.; Bekhtereva, E. S.; Kwabia Tchana, F.

2018-06-01

To determine high-resolution rovibrational levels of the inversion vibrational (v2 = 1) state of the 15NHD2 molecule, the Fourier spectrum in the range from 650 to 1150 cm-1 is studied. The data obtained are used to determine the parameters of the effective Hamiltonian of the examined molecule.

Molecular plasmonics: The role of rovibrational molecular states in exciton-plasmon materials under strong-coupling conditions

NASA Astrophysics Data System (ADS)

Sukharev, Maxim; Charron, Eric

2017-03-01

We extend the model of exciton-plasmon materials to include a rovibrational structure of molecules using wave-packet propagations on electronic potential energy surfaces. Our model replaces conventional two-level emitters with more complex molecules, allowing us to examine the influence of alignment and vibrational dynamics on strong coupling with surface plasmon-polaritons. We apply the model to a hybrid system comprising a thin layer of molecules placed on top of a periodic array of slits. Rigorous simulations are performed for two types of molecular systems described by vibrational bound-bound and bound-continuum electronic transitions. Calculations reveal new features in transmission, reflection, and absorption spectra, including the observation of significantly higher values of the Rabi splitting and vibrational patterns clearly seen in the corresponding spectra. We also examine the influence of anisotropic initial conditions on optical properties of hybrid materials, demonstrating that the optical response of the system is significantly affected by an initial prealignment of the molecules. Our work demonstrates that prealigned molecules could serve as an efficient probe for the subdiffraction characterization of the near-field near metal interfaces.

Excitation of Molecular Hydrogen in the Orion Bar Photodissociation Region from a Deep Near-infrared IGRINS Spectrum

NASA Astrophysics Data System (ADS)

Kaplan, Kyle F.; Dinerstein, Harriet L.; Oh, Heeyoung; Mace, Gregory N.; Kim, Hwihyun; Sokal, Kimberly R.; Pavel, Michael D.; Lee, Sungho; Pak, Soojong; Park, Chan; Sok Oh, Jae; Jaffe, Daniel T.

2017-04-01

We present a deep near-infrared spectrum of the Orion Bar Photodissociation Region (PDR) taken with the Immersion Grating INfrared Spectrometer (IGRINS) on the 2.7 m telescope at the McDonald Observatory. IGRINS has high spectral resolution (R˜ {{45,000}}) and instantaneous broad wavelength coverage (1.45-2.45 μm), enabling us to detect 87 emission lines from rovibrationally excited molecular hydrogen (H2) that arise from transitions out of 69 upper rovibration levels of the electronic ground state. These levels cover a large range of rotational and vibrational quantum numbers and excitation energies, making them excellent probes of the excitation mechanisms of H2 and physical conditions within the PDR. The Orion Bar PDR is thought to consist of cooler high density clumps or filaments (T=50{--}250 K, {n}H={10}5{--}{10}7 cm-3) embedded in a warmer lower density medium (T=250{--}1000 K, {n}H={10}4{--}{10}5 cm-3). We fit a grid of constant temperature and density Cloudy models, which recreate the observed H2 level populations well, to constrain the temperature to a range of 600-650 K and the density to {n}H=2.5× {10}3{--}{10}4 cm-3. The best-fit model gives T = 625 K and {n}H=5× {10}3 cm-3. This well-constrained warm temperature is consistent with kinetic temperatures found by other studies for the Orion Bar’s lower density medium. However, the range of densities well fit by the model grid is marginally lower than those reported by other studies. We could be observing lower density gas than the surrounding medium, or perhaps a density-sensitive parameter in our models is not properly estimated.

Rotational Spectroscopy of the NH3-H2 Molecular Complex

NASA Astrophysics Data System (ADS)

Surin, L. A.; Tarabukin, I. V.; Schlemmer, S.; Breier, A. A.; Giesen, T. F.; McCarthy, M. C.; van der Avoird, A.

2017-03-01

We report the first high resolution spectroscopic study of the NH3-H2 van der Waals molecular complex. Three different experimental techniques, a molecular beam Fourier transform microwave spectrometer, a millimeter-wave intracavity jet OROTRON spectrometer, and a submillimeter-wave jet spectrometer with multipass cell, were used to detect pure rotational transitions of NH3-H2 in the wide frequency range from 39 to 230 GHz. Two nuclear spin species, (o)-NH3-(o)-H2 and (p)-NH3-(o)-H2, have been assigned as carriers of the observed lines on the basis of accompanying rovibrational calculations performed using the ab initio intermolecular potential energy surface (PES) of Maret et al. The experimental spectra were compared with the theoretical bound state results, thus providing a critical test of the quality of the NH3-H2 PES, which is a key issue for reliable computations of the collisional excitation and de-excitation of ammonia in the dense interstellar medium.

Radiative lifetimes of the 2s2p2(4P) metastable levels of N III

NASA Technical Reports Server (NTRS)

Fang, Z.; Kwong, Victor H. S.; Parkinson, W. H.

1993-01-01

The radiative decay rates of N III 175 nm intersystem lines were measured in the laboratory by recording the time dependence of photon intensities emitted as the 2s2p2(4P) metastable term of N(2+) ions decay to the 2s22p(2P0) ground term. A cylindrical radio frequency ion trap was used to store the electron impact-produced N(2+) ions. The radiative decay signals were analyzed by multiexponential least-squares fits to the data. The measured radiative decay rates to the ground term are 1019(+/- 64)/s for 4P sub 1/2, 74.5(+/- 5.4)/s for 4P sub 3/2, and 308( +/- 22)/s for 4P sub 5/2. Comparisons of the measured values with theoretical values are presented.

Experimental and theoretical studies of the npσ1Σu+ and npπ1 Πu+ (n ⩾ 4,N‧ = 1 -6) states of D2: Energies, natural widths, absorption line intensities, and dynamics

NASA Astrophysics Data System (ADS)

Glass-Maujean, M.; Jungen, Ch.; Vasserot, A. M.; Schmoranzer, H.; Knie, A.; Kübler, S.; Ehresmann, A.; Ubachs, W.

2017-08-01

Over a thousand spectral lines in the photoexcitation spectrum of molecular deuterium (D2) to np1 Σu+ and 1Πu+ Rydberg levels (n ⩾ 4) were measured for rotational levels N‧ = 1 -6 in the 117 000-137 000 cm-1 spectral range by two different types of experiments at two synchrotron radiation sources: a vacuum ultraviolet (VUV) Fourier-transform (FT) spectrometer at SOLEIL, Paris and a 10 m-normal-incidence monochromator (NIM) at BESSY II, Berlin. The experimental energies, the absorption cross sections, Einstein A-coefficients, and line widths are compared with ab initio multi-channel quantum defect (MQDT) calculations for these levels. More than 350 R(0) or P(2) lines were assigned, some 280 R(1) or P(3) lines, some 270 R(2) or P(4) lines, over 100 R(3) or P(5) lines, over 90 R(4) lines, and 24 R(5) lines to extract information on the N‧ = 1 -6 excited levels. Transition energies were determined up to excitation energies of 137 000 cm-1 above the ground state, thereby extending earlier work by various authors and considerably improving the spectral accuracy (< 0.1 cm-1), leading to several reassignments. The absorption and the dissociation, ionization and fluorescence excitation cross sections from the NIM experiment are measured on absolute scale and are used to calibrate intensities in the VUV-FT spectra. The overall agreement between experiment and first principles calculations, without adjustable parameters, is excellent in view of the multi-state interferences treated within the MQDT-framework: For the low N‧ values the averaged deviations between those observed in the FT-SOLEIL spectra and those calculated with MQDT are ∼ 0.1 cm-1 with a spread of ∼ 0.5 cm-1. The line intensities in terms of Einstein coefficients are well represented in the MQDT-framework, as are the level widths representing the lifetimes associated with the sum of the three decay channels. These line intensities follow, in general, the 1 /n3 scaling behavior as characteristic in

A comparison of the C III, O V, F VI, and Ne VII Delta n = 0 (2-2) line emissions from a laboratory plasma with theoretical predictions and astrophysical observations

NASA Technical Reports Server (NTRS)

Finkenthal, M.; Yu, . L.; Lippmann, S.; Huang, L. K.; Moos, H. W.; Stratton, B. C.; Bhatia, A. K.

1987-01-01

Spectra of the Delta n = 0 (2-2) transitions of Be I-like ions, C III, O V, F VI, and Ne VII emitted from the TEXT tokamak, were measured with photometrically calibrated instrumentation and compared to the predictions of several models which differ in their treatment of electron impact excitation, using either the distorted wave or R-matrix approach. It was found that the ions from C III to Ne VII were located near the edge of the plasma, at densities between 10 to the 12th and 13th/cu cm. The experimental line ratios were compared with several sets of computations. Agreement is obtained between the experimental data and computations by using the R-matrix technique. This leads to the conclusion that the effect resonances must be included in collision strength calculations, particularly at low nuclear charge. The results show that the line ratios studied may be used with confidence as electron density diagnostics for laboratory or astrophysical plasmas.

Analysis of the coriolis interaction of the ν12 band with 2 ν10 of cis-d 2-ethylene by high-resolution Fourier transform infrared spectroscopy

NASA Astrophysics Data System (ADS)

Goh, K. L.; Tan, T. L.; Ong, P. P.; Teo, H. H.

2000-08-01

The Fourier transform infrared spectrum of the ν12 band of cis-d 2-ethylene ( cis-C 2H 2D 2) has been recorded with an unapodized resolution of 0.0024 cm -1 in the frequency range of 1280-1400 cm -1. This band was found to be mutually coupled by Coriolis interaction with the unobserved 2 ν10 band situated approximately 10 cm -1 below ν12. By fitting a total of 771 infrared transitions of ν12 with a standard deviation of 0.00075 cm -1 using the Watson's Hamiltonian with the inclusion of a c-type Coriolis resonance term, a set of accurate rovibrational constants for V 12=1 state was derived. The ν12 band is A type with a band centre at 1341.1512±0.0001 cm -1. Accurate rovibrational constants for the V 10=2 state were also derived.

Candidate Water Vapor Lines to Locate the H2O Snowline through High-dispersion Spectroscopic Observations. III. Submillimeter H2 16O and H2 18O Lines

NASA Astrophysics Data System (ADS)

Notsu, Shota; Nomura, Hideko; Walsh, Catherine; Honda, Mitsuhiko; Hirota, Tomoya; Akiyama, Eiji; Millar, T. J.

2018-03-01

In this paper, we extend the results presented in our former papers on using ortho-{{{H}}}2{}16{{O}} line profiles to constrain the location of the H2O snowline in T Tauri and Herbig Ae disks, to include submillimeter para-{{{H}}}2{}16{{O}} and ortho- and para-{{{H}}}2{}18{{O}} lines. Since the number densities of the ortho- and para-{{{H}}}2{}18{{O}} molecules are about 560 times smaller than their 16O analogs, they trace deeper into the disk than the ortho-{{{H}}}2{}16{{O}} lines (down to z = 0, i.e., the midplane). Thus these {{{H}}}2{}18{{O}} lines are potentially better probes of the position of the H2O snowline at the disk midplane, depending on the dust optical depth. The values of the Einstein A coefficients of submillimeter candidate water lines tend to be lower (typically <10‑4 s‑1) than infrared candidate water lines. Thus in the submillimeter candidate water line cases, the local intensity from the outer optically thin region in the disk is around 104 times smaller than that in the infrared candidate water line cases. Therefore, in the submillimeter lines, especially {{{H}}}2{}18{{O}} and para-{{{H}}}2{}16{{O}} lines with relatively lower upper state energies (∼a few 100 K) can also locate the position of the H2O snowline. We also investigate the possibility of future observations with ALMA to identify the position of the water snowline. There are several candidate water lines that trace the hot water gas inside the H2O snowline in ALMA Bands 5–10.

Synthesis of mononuclear copper(II) complexes of N3O2 and N4O2 donors containing Schiff base ligands: Theoretical and biological observations

NASA Astrophysics Data System (ADS)

Mancha Madha, K.; Gurumoorthy, P.; Arul Antony, S.; Ramalakshmi, N.

2017-09-01

A new series of six mononuclear copper(II) complexes were synthesized from N3O2 and N4O2 donors containing Schiff base ligands, and characterized by various spectral methods. The geometry of the complexes was determined using UV-Vis, EPR and DFT calculations. The complexes of N3O2 donors (1-3) adopted square pyramidal geometry and the remaining complexes of N4O2 donors (4-6) show distorted octahedral geometry around copper(II) nuclei. Redox properties of the complexes show a one-electron irreversible reduction process in the cathodic potential (Epc) region from -0.74 to -0.98 V. The complexes show potent antioxidant activity against DPPH radicals. Molecular docking studies of complexes showed σ-π interaction, hydrogen bonding, electrostatic and van der Waals interactions with VEGFR2 kinase receptor. In vitro cytotoxicity of the complexes was tested against human breast cancer (MDA-MB-231) cell lines and one normal human dermal fibroblasts (NHDF) cell line through MTT assay. The morphological assessment data obtained by Hoechst 33258 and AO/EB staining revealed that the complexes induce apoptosis pathway of cell death.

O2-O2 and O2-N2 collision-induced absorption mechanisms unravelled

NASA Astrophysics Data System (ADS)

Karman, Tijs; Koenis, Mark A. J.; Banerjee, Agniva; Parker, David H.; Gordon, Iouli E.; van der Avoird, Ad; van der Zande, Wim J.; Groenenboom, Gerrit C.

2018-05-01

Collision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O2 that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O2-O2 and O2-N2, using analytical models and numerical quantum scattering calculations. We unambiguously identify the underlying absorption mechanism, which is shown to depend explicitly on the collision partner—contrary to textbook knowledge. This explains experimentally observed qualitative differences between O2-O2 and O2-N2 collisions in the overall intensity, line shape and vibrational dependence of the absorption spectrum. It is shown that these results can be used to discriminate between conflicting experimental data and even to identify unphysical results, thus impacting future experimental studies and atmospheric applications.

Calibration-quality adiabatic potential energy surfaces for H3(+) and its isotopologues.

PubMed

Pavanello, Michele; Adamowicz, Ludwik; Alijah, Alexander; Zobov, Nikolai F; Mizus, Irina I; Polyansky, Oleg L; Tennyson, Jonathan; Szidarovszky, Tamás; Császár, Attila G

2012-05-14

Calibration-quality ab initio adiabatic potential energy surfaces (PES) have been determined for all isotopologues of the molecular ion H(3)(+). The underlying Born-Oppenheimer electronic structure computations used optimized explicitly correlated shifted Gaussian functions. The surfaces include diagonal Born-Oppenheimer corrections computed from the accurate electronic wave functions. A fit to the 41,655 ab initio points is presented which gives a standard deviation better than 0.1 cm(-1) when restricted to the points up to 6000 cm(-1) above the first dissociation asymptote. Nuclear motion calculations utilizing this PES, called GLH3P, and an exact kinetic energy operator given in orthogonal internal coordinates are presented. The ro-vibrational transition frequencies for H(3)(+), H(2)D(+), and HD(2)(+) are compared with high resolution measurements. The most sophisticated and complete procedure employed to compute ro-vibrational energy levels, which makes explicit allowance for the inclusion of non-adiabatic effects, reproduces all the known ro-vibrational levels of the H(3)(+) isotopologues considered to better than 0.2 cm(-1). This represents a significant (order-of-magnitude) improvement compared to previous studies of transitions in the visible. Careful treatment of linear geometries is important for high frequency transitions and leads to new assignments for some of the previously observed lines. Prospects for further investigations of non-adiabatic effects in the H(3)(+) isotopologues are discussed. In short, the paper presents (a) an extremely accurate global potential energy surface of H(3)(+) resulting from high accuracy ab initio computations and global fit, (b) very accurate nuclear motion calculations of all available experimental line data up to 16,000 cm(-1), and (c) results suggest that we can predict accurately the lines of H(3)(+) towards dissociation and thus facilitate their experimental observation.

Calibration-quality adiabatic potential energy surfaces for H3+ and its isotopologues

NASA Astrophysics Data System (ADS)

Pavanello, Michele; Adamowicz, Ludwik; Alijah, Alexander; Zobov, Nikolai F.; Mizus, Irina I.; Polyansky, Oleg L.; Tennyson, Jonathan; Szidarovszky, Tamás; Császár, Attila G.

2012-05-01

Calibration-quality ab initio adiabatic potential energy surfaces (PES) have been determined for all isotopologues of the molecular ion H_3^+. The underlying Born-Oppenheimer electronic structure computations used optimized explicitly correlated shifted Gaussian functions. The surfaces include diagonal Born-Oppenheimer corrections computed from the accurate electronic wave functions. A fit to the 41 655 ab initio points is presented which gives a standard deviation better than 0.1 cm-1 when restricted to the points up to 6000 cm-1 above the first dissociation asymptote. Nuclear motion calculations utilizing this PES, called GLH3P, and an exact kinetic energy operator given in orthogonal internal coordinates are presented. The ro-vibrational transition frequencies for H_3^+, H2D+, and HD_2^+ are compared with high resolution measurements. The most sophisticated and complete procedure employed to compute ro-vibrational energy levels, which makes explicit allowance for the inclusion of non-adiabatic effects, reproduces all the known ro-vibrational levels of the H_3^+ isotopologues considered to better than 0.2 cm-1. This represents a significant (order-of-magnitude) improvement compared to previous studies of transitions in the visible. Careful treatment of linear geometries is important for high frequency transitions and leads to new assignments for some of the previously observed lines. Prospects for further investigations of non-adiabatic effects in the H_3^+ isotopologues are discussed. In short, the paper presents (a) an extremely accurate global potential energy surface of H_3^+ resulting from high accuracy ab initio computations and global fit, (b) very accurate nuclear motion calculations of all available experimental line data up to 16 000 cm-1, and (c) results suggest that we can predict accurately the lines of H_3^+ towards dissociation and thus facilitate their experimental observation.

SAR study on N2,N4-disubstituted pyrimidine-2,4-diamines as effective CDK2/CDK9 inhibitors and antiproliferative agents† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c8ra01440j

PubMed Central

Jing, Liandong; Tang, Yanbo; Goto, Masuo; Lee, Kuo-Hsiung

2018-01-01

Cyclin-dependent kinases (CDKs) are pivotal kinases in cell cycle transition and gene transcription. A series of N2,N4-diphenylpyrimidine-2,4-diamines were previously identified as potent CDK2/CDK9 inhibitors. To explore the SAR of this structural prototype, twenty-four novel N2,N4-disubstituted pyrimidine-2,4-diamines were designed and synthesized. Among them, twenty-one compounds exhibited potent inhibitory activities against both CDK2/cyclin A and CDK9/cyclin T1 systems, and the most potent CDK2 and CDK9 inhibitors, 3g and 3c, showed IC50 values of 83 nM and 65 nM respectively. Most of these compounds displayed significant inhibition against the tested tumor cell lines in the SRB assay, and in particular, remained active against the triple-negative breast cancer (TNBC) cell line MDA-MB-231. Flow cytometer analysis of compounds 2a, 2d and 3b in MDA-MB-231 cells indicated that these compounds induced cell cycle arrest in G2/M phase. Docking studies on compound 3g were performed, which provided conducive clues for further molecular optimization. PMID:29682280

Band-9 ALMA Observations of the [N II] 122 μm Line and FIR Continuum in Two High-z galaxies.

NASA Astrophysics Data System (ADS)

Ferkinhoff, Carl; Brisbin, Drew; Nikola, Thomas; Stacey, Gordon J.; Sheth, Kartik; Hailey-Dunsheath, Steve; Falgarone, Edith

2015-06-01

We present Atacama Large Millimeter Array (ALMA) observations of two high-redshift systems (SMMJ02399-0136 at z 1 ˜ 2.8 and the Cloverleaf QSO at z 1 ˜ 2.5) in their rest-frame 122 μm continuum (ν sky ˜ 650 GHz, λ sky ˜ 450 μm) and [N ii] 122 μm line emission. The continuum observations with a synthesized beam of ˜0.″ 25 resolve both sources and recover the expected flux. The Cloverleaf is resolved into a partial Einstein ring, while SMMJ02399-0136 is unambiguously separated into two components: a point source associated with an active galactic nucleus and an extended region at the location of a previously identified dusty starburst. We detect the [N ii] line in both systems, though significantly weaker than our previous detections made with the first generation z (Redshift) and Early Universe Spectrometer. We show that this discrepancy is mostly explained if the line flux is resolved out due to significantly more extended emission and longer ALMA baselines than expected. Based on the ALMA observations we determine that ≥75% of the total [N ii] line flux in each source is produced via star formation. We use the [N ii] line flux that is recovered by ALMA to constrain the N/H abundance, ionized gas mass, hydrogen- ionizing photon rate, and star formation rate. In SMMJ02399-0136 we discover it contains a significant amount (˜1000 M ⊙ yr-1) of unobscured star formation in addition to its dusty starburst and argue that SMMJ02399-0136 may be similar to the Antennae Galaxies (Arp 244) locally. In total these observations provide a new look at two well-studied systems while demonstrating the power and challenges of Band-9 ALMA observations of high-z systems.

Suppression of methylmercury-induced MIP-2 expression by N-acetyl-L-cysteine in murine RAW264.7 macrophage cell line.

PubMed

David, Juliet; Nandakumar, Athira; Muniroh, Muflihatul; Akiba, Suminori; Yamamoto, Megumi; Koriyama, Chihaya

2017-11-09

The aim of this study is to examine the inflammatory-cytokine expressions in the presence of non-cytotoxic dose of methylmercury (MeHg) in murine macrophages, which is suspected to play an important role in brain damage caused by MeHg exposure. We focused on murine macrophage inflammatory protein-2 (MIP-2), keratinocyte chemoattractant (KC), and monocyte chemoattractant protein-5 (MCP-5). MIP-2 and KC are murine functional homologues of human IL-8 and MCP-5 for human MCP-1. Furthermore, we examined the suppressive effect of N-acetyl-L-cysteine (NAC) on the MeHg-induced inflammatory cytokines. In a murine RAW264.7 macrophage cell line, MeHg-induced cytokine expressions were measured using real-time PCR. The suppressive effect of NAC was examined by putting it into the culture medium together with MeHg (co-treatment). In addition, pre- and post-treatment experiments were conducted, in which the cells were treated with NAC before and after MeHg exposure, respectively. Exposure to a non-cytotoxic dose of MeHg up-regulated the mRNA expression of MIP-2 and MCP-5. On the other hand, KC expression was not induced in the presence of MeHg. Effect of MeHg on MIP-2 expressions was suppressed by pre-, co-, and post-treatment with NAC. However, the suppressive effect of pre-treatment was less than the post-treatment, which was as effective as co-treatment. In functional homologues of human IL-8, only MIP-2 expression, not KC, was activated in the presence of non-cytotoxic dose of MeHg in murine RAW264.7 macrophage cell line. The more evident inhibitory effect of NAC observed in post-treatment experiments suggests a possible involvement of intracellular activities such as antioxidant effects.

New assignments in the 2 μm transparency window of the 12CH4 Octad band system

NASA Astrophysics Data System (ADS)

Daumont, L.; Nikitin, A. V.; Thomas, X.; Régalia, L.; Von der Heyden, P.; Tyuterev, Vl. G.; Rey, M.; Boudon, V.; Wenger, Ch.; Loëte, M.; Brown, L. R.

2013-02-01

This paper reports new assignments of rovibrational transitions of 12CH4 bands in the range 4600-4887 cm-1 which is usually referred to as a part of the 2 μm methane transparency window. Several experimental data sources for methane line positions and intensities were combined for this analysis. Three long path Fourier transform spectra newly recorded in Reims with 1603 m absorption path length and pressures of 1, 7 and 34 hPa for samples of natural abundance CH4 provided new measurements of 12CH4 lines. Older spectra for 13CH4 (90% purity) from JPL with 73 m absorption path length were used to identify the corresponding lines. Most of the lines in this region belong to the Octad system of 12CH4. The new spectra allowed us to assign 1014 new line positions and to measure 1095 line intensities in the cold bands of the Octad. These new line positions and intensities were added to the global fit of Hamiltonian and dipole moment parameters of the Ground State, Dyad, Pentad and Octad systems. This leads to a noticeable improvement of the theoretical description in this methane transparency window and a better global prediction of the methane spectrum.

Searching for new symmetry species of CH5+ - From lines to states without a model

NASA Astrophysics Data System (ADS)

Brackertz, Stefan; Schlemmer, Stephan; Asvany, Oskar

2017-12-01

CH5+ is a prototype of an extremely flexible molecule for which the quantum states have eluded an analytical description so far. Therefore, the reconstruction of its quantum states relies on methods as e.g. the search for accumulations of combination differences of rovibrational transitions. Using the available high resolution data of the Cologne laboratories [1], this reconstruction has been improved by using the properties of kernel density estimators as well as new combinatorial approaches to evaluate the found accumulations. Two new symmetry sets have been discovered, and the known ones extended, with 1063 of the 2897 measured lines assigned, which is a significant improvement over the 65 assignments of the previous work. This allowed us not only to reconstruct more parts of the ground state levels, but also of the vibrationally excited states of CH5+.

Molecular dynamics simulation of the ionic liquid N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2007-10-11

Thermodynamics, structure, and dynamics of an ionic liquid based on a quaternary ammonium salt with ether side chain, namely, N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, MOENM2E TFSI, are investigated by molecular dynamics (MD) simulations. Average density and configurational energy of simulated MOENM2E TFSI are interpreted with models that take into account empirical ionic volumes. A throughout comparison of the equilibrium structure of MOENM2E TFSI with previous results for the more common ionic liquids based on imidazolium cations is provided. Several time correlation functions are used to reveal the microscopic dynamics of MOENM2E TFSI. Structural relaxation is discussed by the calculation of simultaneous space-time correlation functions. Temperature effects on transport coefficients (diffusion, conductivity, and viscosity) are investigated. The ratio between the actual conductivity and the estimate from ionic diffusion by the Nernst-Einstein equation indicates that correlated motion of neighboring ions in MOENM2E TFSI is similar to imidazolium ionic liquids. In line with experiment, Walden plot of conductivity and viscosity indicates that simulated MOENM2E TFSI should be classified as a poor ionic liquid.

First pressure shift measurement of ozone molecular lines at 9.54 μm using a tunable quantum cascade laser

NASA Astrophysics Data System (ADS)

Minissale, Marco; Zanon-Willette, Thomas; Jeseck, Pascal; Boursier, Corinne; Janssen, Christof

2018-06-01

Using a free-running distributed-feedback quantum cascade laser (QCL) emitting at 9.54 μm, the pressure shift parameters of four intense rovibrational transitions in the ν3 fundamental band of ozone induced by oxygen (O2), air and the noble gases helium (He), argon (Ar), and xenon (Xe) are obtained by employing second harmonic detection. The experimental analysis comprises a full uncertainty budget and provides line shift data which are traceable to SI. The high density of transitions in the ν3 spectral region of ozone make this region particularly difficult to study with more commonly used techniques such as Fourier transform spectroscopy. The comparatively high spectral resolution of the QCL in the MHz range, on the contrary, allows to measure molecular shifts at relatively low pressures (from 2 to 70 hPa), thus reducing the impact of spectral congestion due to pressure broadening of molecular lines. The comparison of our results with published data shows that presently recommended values for the pressure shift are too low in this region. This observation is corroborated by semi-classical calculations using the Robert-Bonamy formalism. A slight negative J dependence, already observed in other ozone vibrational bands, is predicted. Systematic use of our technique could be very useful to support this hypothesis and to make up for the lack of shift parameters for ozone ν3 transitions in molecular spectral databases. A subsequent stabilization of the QCL onto an optical frequency comb will open up possibilities to perform metrological measurements of Doppler-free molecular lines.

Detailed Analysis of Near-IR Water (H2O) Emission in Comet C/2014 Q2 (Lovejoy) with the GIANO/TNG Spectrograph

NASA Astrophysics Data System (ADS)

Faggi, S.; Villanueva, G. L.; Mumma, M. J.; Brucato, J. R.; Tozzi, G. P.; Oliva, E.; Massi, F.; Sanna, N.; Tozzi, A.

2016-10-01

We observed the Oort cloud comet C/2014 Q2 (Lovejoy) on 2015 January 31 and February 1 and 2 at a heliocentric distance of 1.3 au and geocentric distance of 0.8 au during its approach to the Sun. Comet Lovejoy was observed with GIANO, the near-infrared high-resolution spectrograph mounted at the Nasmyth-A focus of the TNG (Telescopio Nazionale Galileo) telescope in La Palma, Canary Islands, Spain. We detected strong emissions of radical CN and water, along with many emission features of unidentified origin, across the 1-2.5 μm region. Spectral lines from eight ro-vibrational bands of H2O were detected, six of them for the first time. We quantified the water production rate [Q(H2O), (3.11 ± 0.14) × 1029 s-1] by comparing the calibrated line fluxes with the Goddard full non-resonance cascade fluorescence model for H2O. The production rates of ortho-water [Q(H2O)ORTHO, (2.33 ± 0.11) × 1029 s-1] and para-water [Q(H2O)PARA, (0.87 ± 0.21) × 1029 s-1] provide a measure of the ortho-to-para ratio (2.70 ± 0.76)). The confidence limits are not small enough to provide a critical test of the nuclear spin temperature.

Detailed Analysis of Near-IR Water (H2O) Emission in Comet C/2014 Q2 (LOVEJOY) with the GIANO/TNG Spectrograph

NASA Technical Reports Server (NTRS)

Faggi, S.; Villanueva, G. L.; Mumma, M. J.; Brucato, J.R.; Tozzi, G. P.; Oliva, E.; Massi, F.; Sanna, N.; Tozzi, A.

2016-01-01

We observed the Oort cloud comet C/2014 Q2 (Lovejoy) on 2015 January 31 and February 1 and 2 at a heliocentric distance of 1.3 au and geocentric distance of 0.8 au during its approach to the Sun. Comet Lovejoy was observed with GIANO, the near-infrared high-resolution spectrograph mounted at the Nasmyth-A focus of the TNG (Telescopio Nazionale Galileo) telescope in La Palma, Canary Islands, Spain. We detected strong emissions of radical CN and water, along with many emission features of unidentified origin, across the 1-2.5 micron region. Spectral lines from eight ro-vibrational bands of H2O were detected, six of them for the first time. We quantified the water production rate [Q(H2O), (3.11+/- 0.14) x 10(exp 29)/s] by comparing the calibrated line fluxes with the Goddard full non-resonance cascade fluorescence model for H2O. The production rates of ortho-water [Q(H2O)ORTHO, (2.33+/- 0.11) x 10(exp 29)/s] and para-water [Q(H2O)PARA, (0.87+/-0.21) x 10(exp 29)/s] provide a measure of the ortho-to-para ratio (2.70+/- 0.76)). The confidence limits are not small enough to provide a critical test of the nuclear spin temperature.

CH3D photomixing spectroscopy up to 2.5 THz: New set of rotational and dipole parameters, first THz self-broadening measurements

NASA Astrophysics Data System (ADS)

Bray, Cédric; Cuisset, Arnaud; Hindle, Francis; Bocquet, Robin; Mouret, Gaël; Drouin, Brian J.

2017-03-01

Several previously unmeasured transitions of 12CH3D have been recorded by a terahertz photomixing continuous-wave spectrometer up to QR(10) branch at 2.5 THz. An improved set of rotational constants has been obtained utilizing a THz frequency metrology based on a frequency comb that achieved an averaged frequency position better than 150 kHz on more than fifty ground-state transitions. A detailed analysis of the measured line intensities was undertaken using the multispectrum fitting program and has resulted in a determination of new dipole moment parameters. Measurements at different pressures of the QR(7) transitions provide the first determination of self-broadening coefficients from pure rotational CH3D lines. The THz rotational measurements are consistent with IR rovibrational data but no significant vibrational dependence of self-broadening coefficient may be observed by comparison.

Line Interference Effects Using a Refined Robert-Bonamy Formalism: the Test Case of the Isotropic Raman Spectra of Autoperturbed N2

NASA Technical Reports Server (NTRS)

Boulet, Christian; Ma, Qiancheng; Thibault, Franck

2014-01-01

A symmetrized version of the recently developed refined Robert-Bonamy formalism [Q. Ma, C. Boulet, and R. H. Tipping, J. Chem. Phys. 139, 034305 (2013)] is proposed. This model takes into account line coupling effects and hence allows the calculation of the off-diagonal elements of the relaxation matrix, without neglecting the rotational structure of the perturbing molecule. The formalism is applied to the isotropic Raman spectra of autoperturbed N2 for which a benchmark quantum relaxation matrix has recently been proposed. The consequences of the classical path approximation are carefully analyzed. Methods correcting for effects of inelasticity are considered. While in the right direction, these corrections appear to be too crude to provide off diagonal elements which would yield, via the sum rule, diagonal elements in good agreement with the quantum results. In order to overcome this difficulty, a re-normalization procedure is applied, which ensures that the off-diagonal elements do lead to the exact quantum diagonal elements. The agreement between the (re-normalized) semi-classical and quantum relaxation matrices is excellent, at least for the Raman spectra of N2, opening the way to the analysis of more complex molecular systems.

The translational, rotational, and vibrational energy effects on the chemical reactivity of water cation H2O+(X 2B1) in the collision with deuterium molecule D2

NASA Astrophysics Data System (ADS)

Xu, Yuntao; Xiong, Bo; Chang, Yih Chung; Ng, C. Y.

2013-07-01

By employing the newly established vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) double quadrupole-double octopole ion guide apparatus, we have examined the translational, rotational, and vibrational energy effects on the chemical reactivity of water cation H2O+(X2B1) in the collision with deuterium molecule D2. The application of a novel electric-field pulsing scheme to the VUV laser PFI-PI ion source has enabled the preparation of a rovibrationally selected H2O+(X2B1; v_1^ + v_2^ + v_3^ +; N+Ka+Kc+) ion beam with not only high internal-state selectivity and high intensity but also high translational energy resolution. Despite the unfavorable Franck-Condon factors, we are able to prepare the excited vibrational states (v_1^ + v_2^ + v_3^ +) = (100) and (020) along with the (000) ground vibrational state, for collisional studies, where v_1^ +, v_2^ +, and v_3^ + represent the symmetric stretching, bending, and asymmetric stretching modes of H2O+(X2B1). We show that a range of rotational levels from N+Ka+Kc+ = 000 to 322, covering a rotational energy range of 0-200 cm-1 of these vibrational states, can also be generated for absolute integral cross section (σ) measurements at center-of-mass collision energies (Ecms) from thermal energies to 10.00 eV. The Ecm dependences of the σ values are consistent with the prediction of the orbiting model, indicating that translational energy significantly hinders the chemical reactivity of H2O+(X2B1). Rotational enhancements are observed at Ecm < 0.30 eV for all the three vibrational states, (000), (100), and (020). While the σ values for (100) are found to be only slightly below those for (000), the σ values for (020) are lower than those for (000) and (100) by up to 20% at Ecm ≤ 0.20 eV, indicative of vibrational inhibition at low Ecm by excitation of the (020) mode. Rationalizations are proposed for the observed rotational enhancements and the bending vibrational inhibition. Rigorous

The (CH2)2O-H2O hydrogen bonded complex. Ab Initio calculations and Fourier transform infrared spectroscopy from neon matrix and a new supersonic jet experiment coupled to the infrared AILES beamline of synchrotron SOLEIL.

PubMed

Cirtog, M; Asselin, P; Soulard, P; Tremblay, B; Madebène, B; Alikhani, M E; Georges, R; Moudens, A; Goubet, M; Huet, T R; Pirali, O; Roy, P

2011-03-31

A series of hydrogen bonded complexes involving oxirane and water molecules have been studied. In this paper we report on the vibrational study of the oxirane-water complex (CH(2))(2)O-H(2)O. Neon matrix experiments and ab initio anharmonic vibrational calculations have been performed, providing a consistent set of vibrational frequencies and anharmonic coupling constants. The implementation of a new large flow supersonic jet coupled to the Bruker IFS 125 HR spectrometer at the infrared AILES beamline of the French synchrotron SOLEIL (Jet-AILES) enabled us to record first jet-cooled Fourier transform infrared spectra of oxirane-water complexes at different resolutions down to 0.2 cm(-1). Rovibrational parameters and a lower bound of the predissociation lifetime of 25 ps for the v(OH)(b) = 1 state have been derived from the rovibrational analysis of the ν(OH)(b) band contour recorded at respective rotational temperatures of 12 K (Jet-AILES) and 35 K (LADIR jet).

Optical pumping by CO2 and n2O lasers - new CW FIR emissions in 1,1-difluoroethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fourrier, M.; Belland, P.; Redon, M.

1985-01-01

Fifty-three new CW FIR laser lines are reported in 1,1-difluoroethane optically pumped near 10 microns by CO2 and N2O lasers. The emission spectrum initially reported in the literature consisted of four lines between 770 and 458 microns and has now been extended to the 2.39 mm-319 micron region. The reason for this extension, especially to the long wavelengths, is analyzed. 12 references.

Diagnostic of N2(A) concentration in high velocity nitrogen afterglow at atmospheric pressure

NASA Astrophysics Data System (ADS)

Pointu, Anne-Marie; Mintusov, Evgeny

2009-10-01

An optical emission diagnostic was used to measure N2(A) concentration in a high velocity (1000 cm/s) N2 flowing afterglow of corona discharge at atmospheric pressure, used for biological decontamination. Introducing impurities of NO (<1e-5) we used two well separated and relatively intense lines of NO gamma and beta bands (248nm and 321 nm), easily studied with a low resolution spectrometer. Based on a simplified transport kinetics, the technique is validated using a variation of lines intensity ratios used as coordinates, for numerous experimental points, measured at different axial distances and for different values of NO injected flow. Moreover, it has been demonstrated that N2(A) creation comes from N+N+N2 atom recombination with a global rate around 2e-33 cm^6/s, a result which agrees with literature, as well as N2(A) loss mechanisms were confirmed to go via quenching with O and N atoms. The order of magnitude of obtained N2(A) concentration, about 1e11 cm-3, coincides with the results of direct measurement (by Vegard-Kaplan band), using a spectrometer of better resolution.

The Syntheses and Structure of the First Vanadium(IV) and Vanadium(V) Binary Azides, V(N3)4, [V(N3)6]2- and [V(N3)6]- (Preprint)

DTIC Science & Technology

2009-11-17

V(N3)3(N3S2)] 2- , [22] have been reported, and no binary vanadium(V) compounds had been known except for VF5, VF6 - and V2O5 . By analogy with...valves. Volatile materials were handled in a Pyrex glass or stainless steel/Teflon-FEP vacuum line. [31] All reaction vessels were passivated with ClF3...successful synthesis of the [V(N3)6] - anion, the only binary vanadium(V) compound known besides VF5, VF6 - and V2O5 . N1’ N8 N9 N1 N2 N3 V N4 N5 N6 N2

Lapatinib sensitivities of two novel trastuzumab-resistant HER2 gene-amplified gastric cancer cell lines.

PubMed

Oshima, Yukiko; Tanaka, Harunari; Murakami, Hiroki; Ito, Yuichi; Furuya, Tomomi; Kondo, Eisaku; Kodera, Yasuhiro; Nakanishi, Hayao

2014-01-01

Trastuzumab (Tmab) resistance is a major clinical problem to be resolved in patients with HER2-positive gastric cancers. However, in contrast to the situation for HER2-positive breast cancer lines, the Tmab-resistant gastric cancer preclinical models that are needed to develop a new therapy to overcome this problem are not yet available. We developed three new cell lines from HER2 gene-amplified gastric cancer cell lines (GLM-1, GLM-4, NCI N-87) by a new in vivo selection method consisting of the repeated culture of small residual peritoneal metastasis but not subcutaneous tumor after Tmab treatment. We then evaluated the anti-tumor efficacy of lapatinib for these Tmab-resistant cells. We successfully isolated two Tmab-resistant cell lines (GLM1-HerR2(3), GLM4-HerR2) among the three tested cell lines. These resistant cells differed from the parental cells in their flat morphology and rapid growth in vitro, but HER2, P95HER2 expression, and Tmab binding were essentially the same for the parental and resistant cells. MUC4 expression was up- or downregulated depending on the cell line. These resistant cells were still sensitive to lapatinib, similar to the parental cells, in vitro. This growth inhibition of the Tmab-resistant cells by lapatinib was due to both G1 cell-cycle arrest and apoptosis induction via effective blockade of the PI3K/Akt and MAPK pathways. A preclinical study confirmed that the Tmab-resistant tumors are significantly susceptible to lapatinib. These results suggest that lapatinib has antitumor activity against the Tmab-resistant gastric cancer cell lines, and that these cell lines are useful for understanding the mechanism of Tmab resistance and for developing a new molecular therapy for Tmab-resistant HER2-positive gastric cancers.

The origin of N III lambda 990 and C III lambda 977 emission in AGN narrow-line region gas

NASA Technical Reports Server (NTRS)

Ferguson, J. W.; Ferland, G. J.; Pradhan, A. K.

1995-01-01

We discuss implications of Hopkins Ultraviolet Telescope (HUT) detections of C III lambda 977 and N III lambda 990 emission from the narrow-line region of the Seyfert 2 galaxy NGC 1068. In their discovery paper Kriss et al. showed that the unexpectedly great strength of these lines implies that the emitting gas must be shock-heated if the lines are collisionally excited. Here we investigate other processes which excite these lines in photoionization equilibrium. Recombination, mainly dielectronic, and continuum fluorescence are strong contributors to the line. The resulting intensities are sensitive to the velocity field of the emitting gas and require that the turbulence be of the same order of magnitude as the observed line width. We propose optical observations that will decide whether the gas is collisionally or radiatively heated.

Spectral shapes of rovibrational lines of CO broadened by He, Ar, Kr and SF6: A test case of the Hartmann-Tran profile

NASA Astrophysics Data System (ADS)

Ngo, N. H.; Lin, H.; Hodges, J. T.; Tran, H.

2017-12-01

High signal-to-noise ratio spectra of the (3-0) band P(1) and P(17) lines of CO broadened by He, Ar, Kr and SF6 were measured with a frequency-stabilized cavity ring-down spectroscopy system. For each collision-partner and both lines, multiple spectra were measured over pressures spanning nearly three decades up to 130 kPa. These data were analyzed with a multispectrum fitting procedure. Line shapes were modeled using the Hartmann-Tran (HT) profile with first-order line mixing as well as several other simplified profiles. The results show that for all considered collision partners (with the exception of SF6), the HT profile captures the measured line shapes with maximum absolute residuals that are within 0.1% of the peak absorption. In the case of SF6, which is the heaviest perturber investigated here, the maximum residuals for the HT profile are twice as large as for the other collision partners.

Spinless hourglass nodal-line semimetals

NASA Astrophysics Data System (ADS)

Takahashi, Ryo; Hirayama, Motoaki; Murakami, Shuichi

2017-10-01

Nodal-line semimetals, one of the topological semimetals, have degeneracy along nodal lines where the band gap is closed. In many cases, the nodal lines appear accidentally, and in such cases it is impossible to determine whether the nodal lines appear or not, only from the crystal symmetry and the electron filling. In this paper, for spinless systems, we show that in specific space groups at 4 N +2 fillings (8 N +4 fillings including the spin degree of freedom), presence of the nodal lines is required regardless of the details of the systems. Here, the spinless systems refer to crystals where the spin-orbit coupling is negligible and the spin degree of freedom can be omitted because of the SU(2) spin degeneracy. In this case the shape of the band structure around these nodal lines is like an hourglass, and we call this a spinless hourglass nodal-line semimetal. We construct a model Hamiltonian as an example and we show that it is always in the spinless hourglass nodal-line semimetal phase even when the model parameters are changed without changing the symmetries of the system. We also establish a list of all the centrosymmetric space groups, under which spinless systems always have hourglass nodal lines, and illustrate where the nodal lines are located. We propose that Al3FeSi2 , whose space-group symmetry is Pbcn (No. 60), is one of the nodal-line semimetals arising from this mechanism.

Study of the Rotational Structure of the v 2 Inversion Band of the 15NH2D Molecule

NASA Astrophysics Data System (ADS)

Fomchenko, A. L.; Belova, A. S.; Kwabia Tchana, F.

2018-04-01

The Fourier spectrum of the 15NH2D molecule in the range from 650 to 1150 cm-1, where the ν2 vibrationinversion band is located, is first studied. Analysis of the given band allows the energy rovibrational structure of the examined state to be determined. The inverse spectroscopic problem is solved based on the data obtained.

A full-dimensional ab initio potential energy surface and rovibrational energies of the Ar–HF complex

NASA Astrophysics Data System (ADS)

Huang, Jing; Zhou, Yanzi; Xie, Daiqian

2018-04-01

We report a new full-dimensional ab initio potential energy surface for the Ar-HF van der Waals complex at the level of coupled-cluster singles and doubles with noniterative inclusion of connected triples levels [CCSD(T)] using augmented correlation-consistent quintuple-zeta basis set (aV5Z) plus bond functions. Full counterpoise correction was employed to correct the basis-set superposition error. The hypersurface was fitted using artificial neural network method with a root mean square error of 0.1085 cm-1 for more than 8000 ab initio points. The complex was found to prefer a linear Ar-H-F equilibrium structure. The three-dimensional discrete variable representation method and the Lanczos propagation algorithm were then employed to calculate the rovibrational states without separating inter- and intra- molecular nuclear motions. The calculated vibrational energies of Ar-HF differ from the experiment values within about 1 cm-1 on the first four HF vibrational states, and the predicted pure rotational energies on (0000) and (1000) vibrational states are deviated from the observed value by about 1%, which shows the accuracy of our new PES.

Solar off-limb line widths: Alfvén waves, ion-cyclotron waves, and preferential heating

NASA Astrophysics Data System (ADS)

Dolla, L.; Solomon, J.

2008-05-01

Context: Alfvén waves and ion-cyclotron absorption of high-frequency waves are frequently brought into models devoted to coronal heating and fast solar-wind acceleration. Signatures of ion-cyclotron resonance have already been observed in situ in the solar wind (HELIOS spacecrafts) and, recently, in the upper corona (UVCS/SOHO remote-sensing results). Aims: We propose a method to constrain both the Alfvén wave amplitude and the preferential heating induced by ion-cyclotron resonance, above a partially developed polar coronal hole observed with the SUMER/SOHO spectrometer. Methods: The instrumental stray light contribution is first substracted from the spectra. By supposing that the non-thermal velocity is related to the Alfvén wave amplitude, it is constrained through a density diagnostic and the gradient of the width of the Mg X 625 Å line. The temperatures of several coronal ions, as functions of the distance above the limb, are then determined by substracting the non-thermal component to the observed line widths. Results: The effect of stray light explains the apparent decrease with height in the width of several spectral lines, this decrease usually starting about 0.1-0.2 R_⊙ above the limb. This result rules out any direct evidence of damping of the Alfvén waves, often suggested by other authors. We also find that the ions with the smallest charge-to-mass ratios are the hottest ones at a fixed altitude and that they are subject to a stronger heating, as compared to the others, between 57´´ and 102´´ above the limb. This constitutes a serious clue to ion-cyclotron preferential heating.

Non-LTE line formation for N: Abundances and stellar parameters. Model atom and first results on BA-type stars

NASA Astrophysics Data System (ADS)

Przybilla, N.; Butler, K.

2001-12-01

A comprehensive model atom for non-LTE line formation calculations for neutral and singly-ionized nitrogen is presented. Highly accurate radiative and collisional atomic data are incorporated, recently determined for astrophysical and fusion research using the R-matrix method in the close-coupling approximation. As a test and first application of the model, nitrogen abundances are determined on the basis of line-blanketed LTE model atmospheres for five stars, the main sequence object Vega (A0 V) and the supergiants eta Leo (A0 Ib), HD 111613 (A2 Iabe), HD 92207 (A0 Iae) and beta Ori (B8 Iae), using high S/N and high-resolution spectra at visual and near-IR wavelengths. The computed non-LTE line profiles fit the observations excellently for a given nitrogen abundance in each object. Moreover, the ionization equilibrium of \\ion{N}{i/ii} proves to be a sensitive temperature indicator for late B-type and early A-type supergiants - even at low metallicities - due to the apparent nitrogen overabundance in these objects. All supergiants within our sample show an enrichment of nitrogen on the order of ~ 0.3-0.6 dex, indicating the mixing of CN-cycled material into atmospheric layers, with the sum of the CNO abundances staying close to solar. This finding is in accordance with recent stellar evolution models accounting for mass-loss and rotation. For Vega, an underabundance of nitrogen by 0.25 dex is found, in good agreement with the similar underabundance of other light elements. The dependence of the non-LTE effects on the atmospheric parameters is discussed with special emphasis on the supergiants where a strong radiation field at low particle densities favours deviations from LTE. Non-LTE effects systematically strengthen the \\ion{N}{i/ii} lines. For some N I lines in supergiants non-LTE abundance corrections in excess of 1 dex are found and they react sensitively to modifications of the collisional excitation data. The influence of microturbulence on the statistical

Binding energies of the ground triplet state a{sup 3}Σ{sub u}{sup +} of Rb{sub 2} and Cs{sub 2} in terms of the generalized Le Roy–Bernstein near-dissociation expansion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sovkov, V. B.; Ivanov, V. S.

Formulae of Le Roy–Bernstein near-dissociation theory are derived in a general isotope–invariant form, applicable to any term in the rotational expansion of a diatomic ro-vibrational term value. It is proposed to use the generalized Le Roy–Bernstein expansion to describe the binding energies (ro-vibrational term values) of the ground triplet state a{sup 3}Σ{sub u}{sup +} of alkali metal dimers. The parameters of this description are determined for Rb{sub 2} and Cs{sub 2} molecules. This approach gives a recipe to calculate the whole variety of the binding energies with characteristic accuracies from ∼1 × 10{sup −3} to 1 × 10{sup −2} cm{supmore » −1} using a relatively simple algebraic equation.« less

Higher titers of some H5N1 and recent human H1N1 and H3N2 influenza viruses in Mv1 Lu vs. MDCK cells

PubMed Central

2011-01-01

Background The infectivity of influenza A viruses can differ among the various primary cells and continuous cell lines used for such measurements. Over many years, we observed that all things equal, the cytopathic effects caused by influenza A subtype H1N1, H3N2, and H5N1 viruses were often detected earlier in a mink lung epithelial cell line (Mv1 Lu) than in MDCK cells. We asked whether virus yields as measured by the 50% tissue culture infectious dose and plaque forming titer also differed in MDCK and Mv1 Lu cells infected by the same influenza virus subtypes. Results The 50% tissue culture infectious dose and plaque forming titer of many influenza A subtype H1N1, H3N2, and H5N1 viruses was higher in Mv1 Lu than in MDCK cells. Conclusions The yields of influenza subtype H1N1, H3N2, and H5N1 viruses can be higher in Mv1 Lu cells than in MDCK cells. PMID:21314955

Pro-neurotensin/neuromedin N expression and processing in human colon cancer cell lines.

PubMed

Rovère, C; Barbero, P; Maoret, J J; Laburthe, M; Kitabgi, P

1998-05-08

The regulatory peptide neurotensin NT has been proposed to exert an autocrine trophic effect on human colon cancers. In the present study, pro-neurotensin/neuromedin N (proNT/NN) expression and processing were investigated in 13 human colon cancer cell lines using a combination of radioimmunoassay and HPLC techniques. All 13 cell lines displayed low to moderate levels of proNT/NN ranging from 10 to 250 fmol/mg protein. However, only 6 (HCT8, LoVo, HT29, C119A, LS174T, and coloDM320) processed the precursor. Three of the latter (HCT8, LS174T, and coloDM320) were analysed in detail with regard to proNT/NN processing pattern and were found to produce NT and large precursor fragments ending with the NT or NN sequence. They had no detectable level of NN. Such a processing pattern resembles that generated by the prohormone convertase PC5. Northern and Western blot analysis of prohormone convertase expression in the 3 cell lines revealed that they were devoid of PC1 and PC2, whereas they all expressed PC5. These data indicate that proNT/NN is a good marker of human colon cancer cell lines while NT is found in only about half of the cell lines. They also suggest that, in addition to NT, several proNT/NN-derived products, possibly generated by PC5, might exert an autocrine positive effect on human colon cancer growth.

First-principles C band absorption spectra of SO2 and its isotopologues

NASA Astrophysics Data System (ADS)

Jiang, Bin; Kumar, Praveen; Kłos, Jacek; Alexander, Millard H.; Poirier, Bill; Guo, Hua

2017-04-01

The low-energy wing of the C ˜ B12 ←X˜ 1A1 absorption spectra for SO2 in the ultraviolet region is computed for the 32S,33S,34S and 36S isotopes, using the recently developed ab initio potential energy surfaces (PESs) of the two electronic states and the corresponding transition dipole surface. The state-resolved absorption spectra from various ro-vibrational states of SO2(X˜ 1A1 ) are computed. When contributions of these excited ro-vibrational states are included, the thermally averaged spectra are broadened but maintain their key characters. Excellent agreement with experimental absorption spectra is found, validating the accuracy of the PESs. The isotope shifts of the absorption peaks are found to increase linearly with energy, in good agreement with experiment.

Anharmonic force field and vibrational dynamics of CH2F2 up to 5000 cm(-1) studied by Fourier transform infrared spectroscopy and state-of-the-art ab initio calculations.

PubMed

Tasinato, Nicola; Regini, Giorgia; Stoppa, Paolo; Pietropolli Charmet, Andrea; Gambi, Alberto

2012-06-07

Difluoromethane (CH(2)F(2), HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 μm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH(2)F(2), providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm(-1). Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm(-1) while intensities are predicted within few km mol(-1) from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν(1)>, |2ν(8)>, |2ν(2)> three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm(-1

Anharmonic force field and vibrational dynamics of CH2F2 up to 5000 cm-1 studied by Fourier transform infrared spectroscopy and state-of-the-art ab initio calculations

NASA Astrophysics Data System (ADS)

Tasinato, Nicola; Regini, Giorgia; Stoppa, Paolo; Charmet, Andrea Pietropolli; Gambi, Alberto

2012-06-01

Difluoromethane (CH2F2, HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 μm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH2F2, providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm-1. Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm-1 while intensities are predicted within few km mol-1 from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν1⟩, |2ν8⟩, |2ν2⟩ three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm-1 region is also

HIV lipodystrophy in participants randomised to lopinavir/ritonavir (LPV/r) +2-3 nucleoside/nucleotide reverse transcriptase inhibitors (N(t)RTI) or LPV/r + raltegravir as second-line antiretroviral therapy.

PubMed

Martin, Allison; Moore, Cecilia L; Mallon, Patrick W G; Hoy, Jennifer F; Emery, Sean; Belloso, Waldo H; Phanuphak, Praphan; Ferret, Samuel; Cooper, David A; Boyd, Mark A

2013-01-01

To compare changes over 48 weeks in body fat, lipids, Metabolic Syndrome and cardiovascular disease risk between patients randomised 1:1 to lopinavir/ritonavir (r/LPV) plus raltegravir (RAL) compared to r/LPV plus 2-3 nucleoside/nucleotide reverse transcriptase inhibitors (N(t)RTIs) as second-line therapy. Participants were HIV-1 positive (>16 years) failing first-line treatment (2 consecutive HIV RNA >500 copies/mL) of NNRTI +2N(t)RTI. Whole body dual energy x-ray absorptiometry was performed at baseline and week 48. Data were obtained to calculate the Metabolic Syndrome and Framingham cardiovascular disease (CVD) risk score. Linear regression was used to compare mean differences between arms. Logistic regression compared incidence of metabolic syndrome. Associations between percent limb fat changes at 48 weeks with baseline variables were assessed by backward stepwise multivariate linear regression. Analyses were adjusted for gender, body mass index and smoking status. 210 participants were randomised. The mean (95% CI) increase in limb fat over 48 weeks was 15.7% (5.3, 25.9) or 0.9 kg (0.2, 1.5) in the r/LPV+N(t)RTI arm and 21.1% (11.1, 31,1) or 1.3 kg (0.7, 1.9) in the r/LPV+RAL arm, with no significant difference between treatment arms (-5.4% [-0.4 kg], p>0.1). Increases in total body fat mass (kg) and trunk fat mass (kg) were also similar between groups. Total:HDL cholesterol ratio was significantly higher in the RAL arm (mean difference -0.4 (1.4); p = 0.03), there were no other differences in lipid parameters between treatment arms. There were no statistically significant differences in CVD risk or incidence of Metabolic Syndrome between the two treatment arms. The baseline predictors of increased limb fat were high viral load, high insulin and participant's not taking lipid lowering treatment. In patients switching to second line therapy, r/LPV combined with RAL demonstrated similar improvements in limb fat as an N(t)RTI + r/LPV regimen, but a worse total

Measurements of Excitation Functions and Line Polarizations for Electron Impact Excitation of the n = 2, 3 States of Atomic Hydrogen in the Energy Range 11 - 2000 eV

NASA Technical Reports Server (NTRS)

James, G. K.; Ajello, J. M.; Kanik, I.; Slevin, J.; Franklin, B.; Shemansky, D.

1993-01-01

The electron-atomic hydrogen scattering system is an important testing ground for theoretical models and has received a great deal of attention from experimentalists and theoreticians alike over the years. A complete description of the excitation process requires a knowledge of many different parameters, and experimental measurements of these parameters have been performed in various laboratories around the world. As far as total cross section data are concerned it has been noted that the discrepancy between the data of Long et al. and Williams for n = 2 excitations needs to be resolved in the interests of any further refinement of theory. We report new measurements of total cross sections and atomic line polarizations for both n=2 and n=3 excitations at energies from threshold to 2000 eV...

Insertion of terminal alkyne into Pt-N bond of the square planar [PtI2(Me2phen)] complex.

PubMed

Benedetti, Michele; De Castro, Federica; Lamacchia, Vincenza; Pacifico, Concetta; Natile, Giovanni; Fanizzi, Francesco P

2017-11-21

The reactivity of [PtX 2 (Me 2 phen)] complexes (X = Cl, Br, I; Me 2 phen = 2,9-dimethyl-1,10-phenanthroline) with terminal alkynes has been investigated. Although the dichlorido species [PtCl 2 (Me 2 phen)] exhibits negligible reactivity, the bromido and iodido derivatives lead in short time to the formation of five-coordinate Pt(ii) complexes of the type [PtX 2 (Me 2 phen)(η 2 -CH[triple bond, length as m-dash]CR)] (X = Br, I; R = Ph, n-Bu), in equilibrium with the starting reagents. Similar to analogous complexes with simple acetylene, the five coordinate species can also undergo dissociation of an halido ligand and formation of the transient square-planar cationic species [PtX(Me 2 phen)(η 2 -CH[triple bond, length as m-dash]CR)] + . This latter can further evolve to give an unusual, sparingly soluble square planar product where the former terminal alkyne is converted into a :C[double bond, length as m-dash]C(H)(R) moiety with the α-carbon bridging the Pt(ii) core with one of the two N-donors of coordinated Me 2 phen. The final product [PtX 2 {κ 2 -N,C-(Z)-N[combining low line]1-N10-C[combining low line][double bond, length as m-dash]C(H)(R)}] (N1-N10 = 2,9-dimethyl-1,10-phenanthroline; X = Br, I) contains a Pt-N-C-C-N-C six-membered chelate ring in a square planar Pt(ii) coordination environment.

H2O absorption spectroscopy for determination of temperature and H2O mole fraction in high-temperature particle synthesis systems.

PubMed

Torek, Paul V; Hall, David L; Miller, Tiffany A; Wooldridge, Margaret S

2002-04-20

Water absorption spectroscopy has been successfully demonstrated as a sensitive and accurate means for in situ determination of temperature and H2O mole fraction in silica (SiO2) particle-forming flames. Frequency modulation of near-infrared emission from a semiconductor diode laser was used to obtain multiple line-shape profiles of H2O rovibrational (v1 + v3) transitions in the 7170-7185-cm(-1) region. Temperature was determined by the relative peak height ratios, and XH2O was determined by use of the line-shape profiles. Measurements were made in the multiphase regions of silane/hydrogen/oxygen/ argon flames to verify the applicability of the diagnostic approach to combustion synthesis systems with high particle loadings. A range of equivalence ratios was studied (phi = 0.47 - 2.15). The results were compared with flames where no silane was present and with adiabatic equilibrium calculations. The spectroscopic results for temperature were in good agreement with thermocouple measurements, and the qualitative trends as a function of the equivalence ratio were in good agreement with the equilibrium predictions. The determinations for water mole fraction were in good agreement with theoretical predictions but were sensitive to the spectroscopic model parameters used to describe collisional broadening. Water absorption spectroscopy has substantial potential as a valuable and practical technology for both research and production combustion synthesis facilities.

N-acetyltransferase 2 activity and folate levels

PubMed Central

Cao, Wen; Strnatka, Diana; McQueen, Charlene A.; Hunter, Robert J.; Erickson, Robert P.

2010-01-01

Aims To determine whether increased N-acetyltransferase (NAT) activity might have a toxic effect during development and an influence on folate levels since previous work has shown that only low levels of exogenous NAT can be achieved in constitutionally transgenic mice (Cao, et al, 2005) Main Methods A human NAT1 tet-inducible construct was used that would not be expressed until the inducer was delivered. Human NAT1 cDNA was cloned into pTRE2 and injected into mouse oocytes. Two transgenic lines were crossed to mouse line TgN(rtTahCMV)4Uh containing the CMV promoted “teton.”Measurements of red blood cell folate levels in inbred strains of mice were performed. Key findings Only low levels of human NAT1 could be achieved in kidney (highly responsive in other studies) whether the inducer, doxycycline, was given by gavage or in drinking water.An inverse correlation of folate levels with Nat2 enzyme activity was found. Significance Since increasing NAT1 activity decrease folate in at least one tissue, the detrimental effect of expression of human NAT1 in combination with endogenous mouse Nat2 may be a consequence of increased catabolism of folate. PMID:19932120

Laboratory measurements of white dwarf photospheric spectral lines: Hβ

DOE PAGES

Falcon, Ross Edward; Rochau, Gregory A.; Bailey, James E.; ...

2015-06-18

We spectroscopically measure multiple hydrogen Balmer line profiles from laboratory plasmas to investigate the theoretical line profiles used in white dwarf (WD) atmosphere models. X-ray radiation produced at the Z Pulsed Power Facility at Sandia National Laboratories initiates plasma formation in a hydrogen-filled gas cell, replicating WD photospheric conditions. We also present time-resolved measurements of Hβ and fit this line using different theoretical line profiles to diagnose electron density, n e, and n = 2 level population, n 2. Aided by synthetic tests, we characterize the validity of our diagnostic method for this experimental platform. During a single experiment, wemore » infer a continuous range of electron densities increasing from n e ~ 4 to ~30 × 10 16 cm -3 throughout a 120-ns evolution of our plasma. Also, we observe n 2 to be initially elevated with respect to local thermodynamic equilibrium (LTE); it then equilibrates within ~55 ns to become consistent with LTE. This also supports our electron-temperature determination of T e ~ 1.3 eV (~15,000 K) after this time. At n e≲ 10 17 cm -3, we find that computer-simulation-based line-profile calculations provide better fits (lower reduced χ 2) than the line profiles currently used in the WD astronomy community. The inferred conditions, however, are in good quantitative agreement. Lastly, this work establishes an experimental foundation for the future investigation of relative shapes and strengths between different hydrogen Balmer lines.« less

Registration of DGE-2, a durum wheat disomic alien substitution line 1E(1A) involving a diploid wheatgrass chromosome

USDA-ARS?s Scientific Manuscript database

The durum wheat (Triticum turgidum L., 2n = 2x = 28; AABB genomes) alien disomic substitution 1E(1A) line DGE-2 (PI 663216) was developed by the USDA–ARS, Cereal Crops Research Unit, Northern Crop Science Laboratory, Fargo, North Dakota and released in 2011. DGE-2 has 2n = 28 chromosomes, which are...

Line intensities and temperature-dependent line broadening coefficients of Q-branch transitions in the v2 band of ammonia near 10.4 μm

NASA Astrophysics Data System (ADS)

Sur, Ritobrata; Spearrin, R. Mitchell; Peng, Wen Y.; Strand, Christopher L.; Jeffries, Jay B.; Enns, Gregory M.; Hanson, Ronald K.

2016-05-01

We report measured line intensities and temperature-dependent broadening coefficients of NH3 with Ar, N2, O2, CO2, H2O, and NH3 for nine sQ(J,K) transitions in the ν2 fundamental band in the frequency range 961.5-967.5 cm-1. This spectral region was chosen due to the strong NH3 absorption strength and lack of spectral interference from H2O and CO2 for laser-based sensing applications. Spectroscopic parameters were determined by multi-line fitting using Voigt lineshapes of absorption spectra measured with two quantum cascade lasers in thermodynamically-controlled optical cells. The temperature dependence of broadening was measured over a range of temperatures between 300 and 600 K. These measurements aid the development of mid-infrared NH3 sensors for a broad range of gas mixtures and at elevated temperatures.

The UV photochemistry of C2N2

NASA Technical Reports Server (NTRS)

Halpern, Joshua B.; Barts, Samuel A.

1989-01-01

The absorption, emission, and photodissociation yield spectra of C2N2 were measured in the 220 and 210 nm region near the 4(0)1 and 1(0)1 4(0)1 bands of the A 1 sigma + from the X 1 sigma + system. The emission spectrum showed very few lines which appeared in the absorption spectrum. Moreover, the emission had 660 ns lifetime and, at 210 nm a very large electronic emission quenching rate. Laser induced fluorescence was used to measure the relative yield of CN radicals as a function of photolysis wavelength. This spectrum seemed to follow the absorption spectrum below the dissociation threshold. Energy in the CN fragments appeared to be statistically distributed.

Broad N2H+ Emission toward the Protostellar Shock L1157-B1

NASA Astrophysics Data System (ADS)

Codella, C.; Viti, S.; Ceccarelli, C.; Lefloch, B.; Benedettini, M.; Busquet, G.; Caselli, P.; Fontani, F.; Gómez-Ruiz, A.; Podio, L.; Vasta, M.

2013-10-01

We present the first detection of N2H+ toward a low-mass protostellar outflow, namely, the L1157-B1 shock, at ~0.1 pc from the protostellar cocoon. The detection was obtained with the IRAM 30 m antenna. We observed emission at 93 GHz due to the J = 1-0 hyperfine lines. Analysis of this emission coupled with HIFI CHESS multiline CO observations leads to the conclusion that the observed N2H+(1-0) line originated from the dense (>=105 cm-3) gas associated with the large (20''-25'') cavities opened by the protostellar wind. We find an N2H+ column density of a few 1012 cm-2 corresponding to an abundance of (2-8) × 10-9. The N2H+ abundance can be matched by a model of quiescent gas evolved for more than 104 yr, i.e., for more than the shock kinematical age (sime2000 yr). Modeling of C-shocks confirms that the abundance of N2H+ is not increased by the passage of the shock. In summary, N2H+ is a fossil record of the pre-shock gas, formed when the density of the gas was around 104 cm-3, and then further compressed and accelerated by the shock.

Inter-laboratory calibration of natural gas round robins for δ2H and δ13C using off-line and on-line techniques

USGS Publications Warehouse

Dai, Jinxing; Xia, Xinyu; Li, Zhisheng; Coleman, Dennis D.; Dias, Robert F.; Gao, Ling; Li, Jian; Deev, Andrei; Li, Jin; Dessort, Daniel; Duclerc, Dominique; Li, Liwu; Liu, Jinzhong; Schloemer, Stefan; Zhang, Wenlong; Ni, Yunyan; Hu, Guoyi; Wang, Xiaobo; Tang, Yongchun

2012-01-01

Compound-specific carbon and hydrogen isotopic compositions of three natural gas round robins were calibrated by ten laboratories carrying out more than 800 measurements including both on-line and off-line methods. Two-point calibrations were performed with international measurement standards for hydrogen isotope ratios (VSMOW and SLAP) and carbon isotope ratios (NBS 19 and L-SVEC CO2). The consensus δ13C values and uncertainties were derived from the Maximum Likelihood Estimation (MLE) based on off-line measurements; the consensus δ2H values and uncertainties were derived from MLE of both off-line and on-line measurements, taking the bias of on-line measurements into account. The calibrated consensus values in ‰ relative to VSMOW and VPDB are: NG1 (coal-related gas): Methane: δ2HVSMOW = − 185.1‰ ± 1.2‰, δ13CVPDB = − 34.18‰ ± 0.10‰ Ethane: δ2HVSMOW = − 156.3‰ ± 1.8‰, δ13CVPDB = − 24.66‰ ± 0.11‰ Propane: δ2HVSMOW = − 143.6‰ ± 3.3‰, δ13CVPDB = − 22.21‰ ± 0.11‰ i-Butane: δ13CVPDB = − 21.62‰ ± 0.12‰ n-Butane: δ13CVPDB = − 21.74‰ ± 0.13‰ CO2: δ13CVPDB = − 5.00‰ ± 0.12‰ NG2 (biogas): Methane: δ2HVSMOW = − 237.0‰ ± 1.2‰, δ13CVPDB = − 68.89‰ ± 0.12‰ NG3 (oil-related gas): Methane: δ2HVSMOW = − 167.6‰ ± 1.0‰, δ13CVPDB = − 43.61‰ ± 0.09‰ Ethane: δ2HVSMOW = − 164.1‰ ± 2.4‰, δ13CVPDB = − 40.24‰ ± 0.10‰ Propane: δ2HVSMOW = − 138.4‰ ± 3.0‰, δ13CVPDB = − 33.79‰ ± 0.09‰ All of the assigned values are traceable to the international carbon isotope standard of VPDB and hydrogen isotope standard of VSMOW.

Preliminary assignments of 2 ν 3 - ν 4 hot band of 12 CH 4 in the 2 μm transparency window from long-path FTS spectra

NASA Astrophysics Data System (ADS)

Nikitin, A. V.; Daumont, L.; Thomas, X.; Régalia, L.; Rey, M.; Tyuterev, Vl. G.; Brown, L. R.

2011-07-01

New measurements and assignments for the rovibrational transitions of the hot band 2 v3- v4 of 12CH 4 are reported from 4600 to 4880 cm -1 and refer to lower part of the 2 μm methane transparency window. Three long-path spectra were recorded with a Fourier transform spectrometer (FTS) in Reims using an L = 1603 m absorption path length at 1, 7, 34 h Pa for the natural samples of CH 4; a spectrum of enriched 13CH 4 was also used. Assignments were made for 196 lines of 2 v3(F 2,E)- v4. These transitions had an integrated intensity of 5 × 10 -24 cm/molecule at 296 K and improved the overall description of absorption in the 2.1 μm region. The empirical upper state levels of these assignments belong to Tetradecad (4800-6200 cm -1). The new analysis provided much better accuracies of badly blended positions of 2 v3(F 2)-ground state manifolds at 1.66 μm.

VUV Fourier-transform absorption study of the Lyman and Werner bands in D2

NASA Astrophysics Data System (ADS)

de Lange, Arno; Dickenson, Gareth D.; Salumbides, Edcel J.; Ubachs, Wim; de Oliveira, Nelson; Joyeux, Denis; Nahon, Laurent

2012-06-01

An extensive survey of the D2 absorption spectrum has been performed with the high-resolution VUV Fourier-transform spectrometer employing synchrotron radiation. The frequency range of 90 000-119 000 cm-1 covers the full depth of the potential wells of the B sideset{^1}{+u}{Σ}, B^' } sideset{^1}{+u}{Σ}, and C 1Πu electronic states up to the D(1s) + D(2ℓ) dissociation limit. Improved level energies of rovibrational levels have been determined up to respectively v = 51, v = 13, and v = 20. Highest resolution is achieved by probing absorption in a molecular gas jet with slit geometry, as well as in a liquid helium cooled static gas cell, resulting in line widths of ≈0.35 cm-1. Extended calibration methods are employed to extract line positions of D2 lines at absolute accuracies of 0.03 cm-1. The D 1Πu and B^' ' } sideset{^1}{+u}{Σ} electronic states correlate with the D(1s) + D(3ℓ) dissociation limit, but support a few vibrational levels below the second dissociation limit, respectively, v = 0-3 and v = 0-1, and are also included in the presented study. The complete set of resulting level energies is the most comprehensive and accurate data set for D2. The observations are compared with previous studies, both experimental and theoretical.

Ecdysteroid-stimulated synthesis and secretion of an N-acetyl-D-glucosamine-rich glycopeptide in a lepidopteran cell line derived from imaginal discs.

PubMed

Porcheron, P; Morinière, M; Coudouel, N; Oberlander, H

1991-01-01

Hormone-regulated processing of N-acetyl-D-glucosamine was studied in an insect cell line derived from imaginal wing discs of the Indian meal moth, Plodia interpunctella (Hübner). The cell line, IAL-PID2, responded to treatment with 20-hydroxyecdysone with increased incorporation of GlcNAc into glycoproteins. Cycloheximide and tunicamycin counteracted the action of the hormone. In particular, treatment with 20-hydroxyecdysone resulted in the secretion of a 5,000 dalton N-acetyl-D-glucosamine-rich glycopeptide by the IAL-PID2 cells. Accumulation of this peptide was prevented by the use of teflubenzuron, a potent chitin synthesis inhibitor. A glycopeptide of similar molecular weight was observed in imaginal discs of P. interpunctella treated with 20-hydroxyecdysone in vitro, under conditions that induce chitin synthesis. Although the function of the 5,000 dalton glycopeptide is not known, we believe that the PID2 cell line is a promising model for molecular analysis of ecdysteroid-regulated processing of aminosugars by epidermal cells during insect development.

Numerical simulations of sheared magnetic lines at the solar null line

NASA Astrophysics Data System (ADS)

Kuźma, B.; Murawski, K.; Solov'ev, A.

2015-05-01

Aims: We perform numerical simulations of sheared magnetic lines at the magnetic null line configuration of two magnetic arcades that are settled in a gravitationally stratified and magnetically confined solar corona. Methods: We developed a general analytical model of a 2.5D solar atmospheric structure. As a particular application of this model, we adopted it for the curved magnetic field lines with an inverted Y shape that compose the null line above two magnetic arcades, which are embedded in the solar atmosphere that is specified by the realistic temperature distribution. The physical system is described by 2.5D magnetohydrodynamic equations that are numerically solved by the FLASH code. Results: The magnetic field line shearing, implemented about 200 km below the transition region, results in Alfvén and magnetoacoustic waves that are able to penetrate solar coronal regions above the magnetic null line. As a result of the coupling of these waves, partial reflection from the transition region and scattering from inhomogeneous regions the Alfvén waves experience fast attenuation on time scales comparable to their wave periods, and the physical system relaxes in time. The attenuation time grows with the large amplitude and characteristic growing time of the shearing. Conclusions: By having chosen a different magnetic flux function, the analytical model we devised can be adopted to derive equilibrium conditions for a diversity of 2.5D magnetic structures in the solar atmosphere. Movie associated to Fig. 5 is available in electronic form at http://www.aanda.org

The Rovibrational Intensities of Five Absorption Bands of (12)C(16)O2 Between 5218 and 5349/cm

NASA Technical Reports Server (NTRS)

Giver, Lawrence P.; Brown, Linda R.; Chackerian, Charles, Jr.; Freedman, Richard S.; Gore, Warren J. (Technical Monitor)

2002-01-01

Absolute line intensities, band intensities, and Herman-Wallis parameters were measured for the (01(sup 1)2)(sub I) from (00(sup 0)0)(sub I) perpendicular band of (12)C(16)O2 centered at 5315/cm, along with the three nearby associated hot bands: (10(sup 0)2)(sub II) from (01(sup 1)0)(sub I) at 5248/cm, (02(sup 2))(sub I) from (01(sup 1)0)(sub I) at 5291/cm, and (10(sup 0)2)(sub I) from (01(sup 1)0)(sub I) at 5349/cm. The nearby parallel hot band (30(sup 0))(sub I) from (10(sup 0)0)(sub II) at 5218/cm was also included in this study.

Line mixing calculation in the ν 6Q-branches of N 2-broadened CH 3Br at low temperatures

NASA Astrophysics Data System (ADS)

Gomez, L.; Tran, H.; Jacquemart, D.

2009-07-01

In an early study [H. Tran, D. Jacquemart, J.Y. Mandin, N. Lacome, JQSRT 109 (2008) 119-131], line mixing effects of the ν 6 band of methyl bromide were observed and modeled at room temperature. In the present work, line mixing effects have been considered at low temperatures using state-to-state collisional rates which were modeled by a fitting law based on the energy gap and a few fitting parameters. To validate the model, several spectra of methyl bromide perturbed by nitrogen have been recorded at various temperatures (205-299 K) and pressures (230-825 hPa). Comparisons between measured spectra and calculations using both direct calculation from relaxation operator and Rosenkranz profile have been performed showing improvement compared to the usual Lorentz profile. Note that the temperature dependence of the spectroscopic parameters has been taken into account using results of previous studies.

Astronomical Applications of New Line Lists for CN, C_2 and Their Isotopologues

NASA Astrophysics Data System (ADS)

Bernath, Peter F.; Sneden, Chris; Brooke, James S. A.; Ram, Ram

2014-06-01

For cool stellar and substellar objects, atomic lines weaken, and detailed elemental and isotopic abundances are often derived from molecular absorption features. We have embarked on a project to provide molecular line lists by combining experimental observations for line positions with ab initio calculations for line strengths. So far we have results for MgH (A-X and B-X transitions), C2 (Swan system), CP (A-X transition), NH (vibration-rotation bands) and OH (Meinel system). This talk will briefly describe the new line lists for the Swan system (d3Π-a3Π) of C2 and 12C13C, and the red (A2Π-X2Σ+) and violet (B2Σ+-X2Σ+) systems of CN, 13CN and C15N. Applications to the spectra of carbon-enhanced metal-poor stars, the K-giant Arcturus, the metal-rich open cluster NGC 6791, the Sun and comets will be presented. E. GharibNezhad, A. Shayesteh and P. F. Bernath, Mon. Notices R. Astro. Soc. 432, 2043-2047 (2013) . H. Hinkle, L. Wallace, R. S. Ram, P. F. Bernath, C. Sneden and S. Lucatello, Astrophys. J. Suppl. 207, 26 (7pp) (2013) J. S. A. Brooke, P. F. Bernath, T. W. Schmidt and G. B. Bacskay, J. Quant. Spectrosc. Rad. Trans. 124, 11-20 (2013) R. S. Ram, J. S. A. Brooke, P. F. Bernath, C. Sneden and S. Lucatello, Astrophys. J. Suppl. 211, 5 (7pp) (2014) J. S. A. Brooke, R. S. Ram, C. M. Western, G. Li, D. W. Schwenke and P. F. Bernath, Astrophys. J. Suppl. 210, 23 (15pp) (2014) R. S. Ram, J. S. A. Brooke, C.M. Western and P. F. Bernath, J. Quant. Spectrosc. Rad. Transfer (in press) J. S. A. Brooke et al., this meeting, P301

The GBT PRIMOS Project - A Broadband Spectral Line Survey of SgrB2N from 300 MHz to 46 GHz

NASA Astrophysics Data System (ADS)

Remijan, Anthony J.; Hollis, J. M.; Jewell, P. R.; Lovas, F.; Corby, J.

2013-01-01

Broadband, very sensitive, high spectral resolution spectral line surveys in recent years have made profound impacts into the understanding of interstellar reaction processes and in the identification of new molecular material in astronomical environments. Molecular line surveys are studies of the spectra of astronomical sources over a wide and usually continuous range of frequencies in order to determine the chemical composition (i.e., "molecular inventory"), physical properties (temperature, density), and kinematics of such regions. The National Radio Astronomy Observatory's (NRAO) 100-m Robert C. Byrd Green Bank Telescope (GBT) PRebiotic Interstellar MOlecule Survey (PRIMOS) Legacy Project started in Jan 2008 and concluded in July 2011. The PRIMOS project recorded a nearly frequency-continuous astronomical spectrum from 300 MHz to 46 GHz towards the Sgr B2(N) molecular cloud, with the pointing position centered on the Large Molecule Heimat (LMH). The PRIMOS data have resulted in numerous new detections and discoveries in astrochemistry. The data have also been widely used to demonstrate advances in molecular astrophysics in a variety of venues and have been instrumental in training the next generation of astronomers and chemists. The GBT is the only telescope in the world capable of making these groundbreaking discoveries. This presentation will highlight the recent successes from the survey and how to access these publically-available observations.

First infrared high resolution analysis of the ν5 band of phosgene 37Cl2CO

NASA Astrophysics Data System (ADS)

Flaud, J.-M.; Kwabia Tchana, F.; Perrin, A.; Manceron, L.; Ndao, M.

2018-06-01

A Fourier transform spectrum of phosgene (Cl2CO) has been recorded in the 11.8 μm spectral region at low temperature and at a resolution of 0.00102 cm-1 using a Bruker IFS125HR spectrometer coupled to synchrotron radiation leading to the observation of the ν5 vibrational band of the isotopologue 37Cl2CO. The corresponding upper state rovibrational levels were fit using a Watson-type Hamiltonian. In this way it was possible to reproduce the upper state rovibrational levels almost to within the experimental uncertainty i.e. ∼0.50 × 10-3 cm-1. Very accurate rotational and centrifugal distortion constants were derived from the fit together with the following band center: ν0 (ν5,37Cl2CO) = 848.970769 (20) cm-1.

Transition dipole-moment of the ν1 +ν3 band of acetylene measured with dual-comb Fourier-transform spectroscopy

NASA Astrophysics Data System (ADS)

Okubo, Sho; Iwakuni, Kana; Yamada, Koichi M. T.; Inaba, Hajime; Onae, Atsushi; Hong, Feng-Lei; Sasada, Hiroyuki

2017-11-01

The ν1 +ν3 vibration band of acetylene (C2H2) in the near infrared region was recorded with a dual-comb Fourier-transform spectrometer. We observed 56 transitions from P (26) to R (29) at six different column densities. The integral line intensity was determined for each recorded absorption line by fitting the line profile to Lambert-Beer's law with a Voigt function. Thanks to the outstanding capability of dual-comb spectroscopy to cover a broad spectrum in a relatively short time with high resolution and high frequency precision, we determined the reliable line strength for each ro-vibrational transition as well as the transition dipole moment for this band.

LABORATORY MEASUREMENTS OF WHITE DWARF PHOTOSPHERIC SPECTRAL LINES: Hβ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Falcon, Ross E.; Gomez, T. A.; Montgomery, M. H.

2015-06-20

We spectroscopically measure multiple hydrogen Balmer line profiles from laboratory plasmas to investigate the theoretical line profiles used in white dwarf (WD) atmosphere models. X-ray radiation produced at the Z Pulsed Power Facility at Sandia National Laboratories initiates plasma formation in a hydrogen-filled gas cell, replicating WD photospheric conditions. Here we present time-resolved measurements of Hβ and fit this line using different theoretical line profiles to diagnose electron density, n{sub e}, and n = 2 level population, n{sub 2}. Aided by synthetic tests, we characterize the validity of our diagnostic method for this experimental platform. During a single experiment, wemore » infer a continuous range of electron densities increasing from n{sub e} ∼ 4 to ∼30 × 10{sup 16} cm{sup −3} throughout a 120-ns evolution of our plasma. Also, we observe n{sub 2} to be initially elevated with respect to local thermodynamic equilibrium (LTE); it then equilibrates within ∼55 ns to become consistent with LTE. This supports our electron-temperature determination of T{sub e} ∼ 1.3 eV (∼15,000 K) after this time. At n{sub e} ≳ 10{sup 17} cm{sup −3}, we find that computer-simulation-based line-profile calculations provide better fits (lower reduced χ{sup 2}) than the line profiles currently used in the WD astronomy community. The inferred conditions, however, are in good quantitative agreement. This work establishes an experimental foundation for the future investigation of relative shapes and strengths between different hydrogen Balmer lines.« less

Carbon Chemistry in IRC+10216: Infrared Detection of Diacetylene

NASA Astrophysics Data System (ADS)

Fonfría, J. P.; Agúndez, M.; Cernicharo, J.; Richter, M. J.; Lacy, J. H.

2018-01-01

We present the detection of C4H2 for first time in the envelope of the C-rich AGB star IRC+10216, based on high spectral resolution mid-infrared observations carried out with the Texas Echelon-cross-Echelle Spectrograph mounted on the Infrared Telescope Facility. The obtained spectrum contains 24 narrow absorption features above the detection limit, identified as lines of the ro-vibrational C4H2 band {ν }6+{ν }8({σ }u+). The analysis of these lines through a ro-vibrational diagram indicates that the column density of C4H2 is (2.4 ± 1.5) × 1016 cm‑2. Diacetylene is distributed in two excitation populations accounting for 20% and 80% of the total column density and with rotational temperatures of 47 ± 7 and 420 ± 120 K, respectively. This two-folded rotational temperature suggests that the absorbing gas is located beyond ≃0.″4 ≃ 20 R ⋆ from the star, with a noticeable cold contribution outwards from ≃10″ ≃ 500 R ⋆. This outer shell matches up with the place where cyanoacetylenes and carbon chains are known to form due to the action of the Galactic dissociating radiation field on the neutral gas coming from the inner layers of the envelope.

The structure, stability, and infrared spectrum of B 2N, B 2N +, B 2N -, BO, B 2O and B 2N 2.

NASA Astrophysics Data System (ADS)

Martin, J. M. L.; François, J. P.; Gijbels, R.

1992-05-01

The structure, infrared spectrum, and heat of formation of B 2N, B 2N -, BO, and B 2O have been studied ab initio. B 2N is very stable; B 2O even more so. B 2N, B 2N -, B 2O, and probably B 2N + have symmetric linear ground-state structures; for B 2O, an asymmetric linear structure lies about 12 kcal/mol above the ground state. B 2N +, B 2N - and B 2O have intense asymmetric stretching frequencies, predicted near 870, 1590 and 1400 cm -1, respectively. Our predicted harmonic frequencies and isotopic shifts for B 2O confirm the recent experimental identification by Andrews and Burkholder. Absorptions at 1889.5 and 1998.5 cm -1 in noble-gas trapped boron nitride vapor belong the BNB and BNBN ( 3Π), respectively; a tentative assignment of 882.5 cm -1 to BNB + is proposed. Total atomization energies Σ De (Σ D0) are computed (accuracy ±2 kcal/mol) as: BO 193.1 (190.4), B 2O 292.5 (288.7), B 2N 225.0 (250.3) kcal/mol. The ionization potential and electron affinity of B 2N are predicted to be 8.62±0.1 and 3.34±0.1 eV. The MP4-level additivity approximations involved in G1 theory results in errors on the order of 1 kcal/mol in the Σ De values.

Line-by-line spectroscopic simulations on graphics processing units

NASA Astrophysics Data System (ADS)

Collange, Sylvain; Daumas, Marc; Defour, David

2008-01-01

We report here on software that performs line-by-line spectroscopic simulations on gases. Elaborate models (such as narrow band and correlated-K) are accurate and efficient for bands where various components are not simultaneously and significantly active. Line-by-line is probably the most accurate model in the infrared for blends of gases that contain high proportions of H 2O and CO 2 as this was the case for our prototype simulation. Our implementation on graphics processing units sustains a speedup close to 330 on computation-intensive tasks and 12 on memory intensive tasks compared to implementations on one core of high-end processors. This speedup is due to data parallelism, efficient memory access for specific patterns and some dedicated hardware operators only available in graphics processing units. It is obtained leaving most of processor resources available and it would scale linearly with the number of graphics processing units in parallel machines. Line-by-line simulation coupled with simulation of fluid dynamics was long believed to be economically intractable but our work shows that it could be done with some affordable additional resources compared to what is necessary to perform simulations on fluid dynamics alone. Program summaryProgram title: GPU4RE Catalogue identifier: ADZY_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADZY_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 62 776 No. of bytes in distributed program, including test data, etc.: 1 513 247 Distribution format: tar.gz Programming language: C++ Computer: x86 PC Operating system: Linux, Microsoft Windows. Compilation requires either gcc/g++ under Linux or Visual C++ 2003/2005 and Cygwin under Windows. It has been tested using gcc 4.1.2 under Ubuntu Linux 7.04 and using Visual C

Absorption of solar radiation by O2 - Implications for O3 and lifetimes of N2O, CFCl3, and CF2Cl2

NASA Technical Reports Server (NTRS)

Minschwaner, K.; Salawitch, R. J.; Mcelroy, M. B.

1993-01-01

An accurate line-by-line model is used to evaluate effects of absorption in the Schumann-Runge bands of O2 on transmission of UV radiation. The model is used to evaluate rates of photolysis for N2O, CFCl3, and CF2Cl2, and to infer global loss rates and instantaneous lifetimes appropriate for 1980. A parameterized version of the line-by-line model enabling rapid evaluation of transmission in the Schumann-Runge region is described. Photochemical calculations employing the parameterization and constrained by data from the Atmospheric Trace Molecule Spectroscopy experiment are used to examine the budget of odd oxygen. Consistent with previous studies, it is shown that photochemical loss of odd oxygen exceeds production by photolysis of O2 for altitudes above 40 km. The imbalance between production and loss is shown to be consistent with a source of odd oxygen proportional to the product of the mixing ratio and photolysis rate of ozone, which suggests that processes involving vibrationally excited O2 may play an important role in production of odd oxygen.

Emission-line studies of young stars. 4: The optical forbidden lines

NASA Technical Reports Server (NTRS)

Hamann, Fred

1994-01-01

Optical forbidden line strengths and profiles are discussed for a sample of 30 T Tauri stars and 12 Herbig Ae-Be stars. Transitions of (C I), (N II), (O I), (O II), (S II), (Ca II), (Cr II), (Fe II), and (Ni II) are detected. Profile variability occurred in DG Tau and probably other sources. The ensemble profiles can be divided into four generic components that may represent distinct emitting regions; (1) narrow rest-velocity lines, (2) 'low'-velocity lines (peaking at less than or approximately +/- 50 km s(exp -1)), (3) 'high'-velocity (usually greater than or approximately +/- 100 km s(exp -1)) blueshifted peaks or wings, and (4) high-velocity redshifted peaks. Among T Tauri stars, the rest-velocity lines appear most often in sources with weak and narrow permitted lines, such as the Ca II triplet. The low- and high-velocity blueshifted components usually appear together in sources with strong and broad Ca II triplet lines. If the velocity-shifted lines form in jets, the smallest (full) opening angles required by the profiles are less than or approximately 20 deg for the narrow, blueshifted (Ca II) lines of DG Tau and HL Tau. Other lines in DG Tau are much broader, implying larger opening angles or greater velocity dispersions. The variability in DG Tau also implies significant changes in the collimation or velocity coherence on timescales of a few years. RW Aur and AS 353A have blue- and redshifted line peaks that could form in oppositely directed jets. The strong (S II) lambda 6716 and lambda 6731 lines in RW Aur are exclusively redshifted and require opening angles less than or approximately 60 deg. Measurements of different profiles in the same spectrum show that the physical conditions change with the line-of-sight velocities. The most persistent trends are for more (N II) and (O II) and less (O I) lambda 5577 flux at high velocities. Constraints on the physical conditions are derived by modeling the emission lines via multilevel ions in 'coronal ionization

A study of the H2O absorption line shifts in the visible spectrum region due to air pressure

NASA Technical Reports Server (NTRS)

Grossmann, B. E.; Browell, E. V.; Bykov, A. D.; Kapitanov, V. A.; Korotchenko, E. A.

1990-01-01

Results of measured and calculated shift coefficients are presented for 170 absorption lines of H2O in five vibrational-rotational bands. The measurements have been carried out using highly sensitive laser spectrometers with a resolution of at least 0.01/cm; the calculations are based on the Anderson-Tsao-Curnutte-Frost method. Good agreement is obtained between the theoretical and experimental values of the shift coefficients of H2O lines due to N2, O2, and air pressure.

The Abundance of C2H4 in the Circumstellar Envelope of IRC+10216.

PubMed

Fonfría, J P; Hinkle, K H; Cernicharo, J; Richter, M J; Agúndez, M; Wallace, L

2017-02-01

High spectral resolution mid-IR observations of ethylene (C 2 H 4 ) towards the AGB star IRC+10216 were obtained using the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infrared Telescope Facility (IRTF). Eighty ro-vibrational lines from the 10.5 µ m vibrational mode ν 7 with J ≲ 30 were detected in absorption. The observed lines are divided into two groups with rotational temperatures of 105 and 400 K (warm and hot lines). The warm lines peak at ≃ -14 km s -1 with respect to the systemic velocity, suggesting that they are mostly formed outwards from ≃ 20 R ⋆ . The hot lines are centered at -10 km s -1 indicating that they come from a shell between 10 and 20 R ⋆ . 35% of the observed lines are unblended and can be fitted with a code developed to model the emission of a spherically symmetric circumstellar envelope. The analysis of several scenarios reveal that the C 2 H 4 abundance relative to H 2 in the range 5 - 20 R ⋆ is 6.9 × 10 -8 in average and it could be as high as 1.1 × 10 -7 . Beyond 20 R ⋆ , it is 8.2 × 10 -8 . The total column density is (6.5 ± 3.0) × 10 15 cm -2 . C 2 H 4 is found to be rotationally under local thermodynamical equilibrium (LTE) and vibrationally out of LTE. One of the scenarios that best reproduce the observations suggests that up to 25% of the C 2 H 4 molecules at 20 R ⋆ could condense onto dust grains. This possible depletion would not influence significantly the gas acceleration although it could play a role in the surface chemistry on the dust grains.

The Abundance of C2H4 in the Circumstellar Envelope of IRC+10216

PubMed Central

Fonfría, J. P.; Hinkle, K. H.; Cernicharo, J.; Richter, M. J.; Agúndez, M.

2017-01-01

High spectral resolution mid-IR observations of ethylene (C2H4) towards the AGB star IRC+10216 were obtained using the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infrared Telescope Facility (IRTF). Eighty ro-vibrational lines from the 10.5 µm vibrational mode ν7 with J ≲ 30 were detected in absorption. The observed lines are divided into two groups with rotational temperatures of 105 and 400 K (warm and hot lines). The warm lines peak at ≃ −14 km s−1 with respect to the systemic velocity, suggesting that they are mostly formed outwards from ≃ 20R⋆. The hot lines are centered at −10 km s−1 indicating that they come from a shell between 10 and 20R⋆. 35% of the observed lines are unblended and can be fitted with a code developed to model the emission of a spherically symmetric circumstellar envelope. The analysis of several scenarios reveal that the C2H4 abundance relative to H2 in the range 5 − 20R⋆ is 6.9 × 10−8 in average and it could be as high as 1.1 × 10−7. Beyond 20R⋆, it is 8.2 × 10−8. The total column density is (6.5 ± 3.0) × 1015 cm−2. C2H4 is found to be rotationally under local thermodynamical equilibrium (LTE) and vibrationally out of LTE. One of the scenarios that best reproduce the observations suggests that up to 25% of the C2H4 molecules at 20R⋆ could condense onto dust grains. This possible depletion would not influence significantly the gas acceleration although it could play a role in the surface chemistry on the dust grains. PMID:28184097

Detection of amino acetonitrile in Sgr B2(N)

NASA Astrophysics Data System (ADS)

Belloche, A.; Menten, K. M.; Comito, C.; Müller, H. S. P.; Schilke, P.; Ott, J.; Thorwirth, S.; Hieret, C.

2008-04-01

Context: Amino acids are building blocks of proteins and therefore key ingredients for the origin of life. The simplest amino acid, glycine (NH2CH2COOH), has long been searched for in the interstellar medium but has not been unambiguously detected so far. At the same time, more and more complex molecules have been newly found toward the prolific Galactic center source Sagittarius B2. Aims: Since the search for glycine has turned out to be extremely difficult, we aimed at detecting a chemically related species (possibly a direct precursor), amino acetonitrile (NH2CH2CN). Methods: With the IRAM 30 m telescope we carried out a complete line survey of the hot core regions Sgr B2(N) and (M) in the 3 mm range, plus partial surveys at 2 and 1.3 mm. We analyzed our 30 m line survey in the LTE approximation and modeled the emission of all known molecules simultaneously. We identified spectral features at the frequencies predicted for amino acetonitrile lines having intensities compatible with a unique rotation temperature. We also used the Very Large Array to look for cold, extended emission from amino acetonitrile. Results: We detected amino acetonitrile in Sgr B2(N) in our 30 m telescope line survey and conducted confirmatory observations of selected lines with the IRAM Plateau de Bure and the Australia Telescope Compact Array interferometers. The emission arises from a known hot core, the Large Molecule Heimat, and is compact with a source diameter of 2 arcsec (0.08 pc). We derived a column density of 2.8 × 1016 cm-2, a temperature of 100 K, and a linewidth of 7 km s-1. Based on the simultaneously observed continuum emission, we calculated a density of 1.7 × 108 cm-3, a mass of 2340 M_⊙, and an amino acetonitrile fractional abundance of 2.2 × 10-9. The high abundance and temperature may indicate that amino acetonitrile is formed by grain surface chemistry. We did not detect any hot, compact amino acetonitrile emission toward Sgr B2(M) or any cold, extended emission

A Survey of Metal Lines at High Redshift. II. SDSS Absorption Line Studies—O VI Line Density, Space Density, and Gas Metallicity at z abs ~ 3.0

NASA Astrophysics Data System (ADS)

Frank, S.; Mathur, S.; Pieri, M.; York, D. G.

2010-09-01

We have analyzed a large data set of O VI absorber candidates found in the spectra of 3702 Sloan Digital Sky Survey (SDSS) quasars, focusing on a subsample of 387 active galactic nuclei sight lines with an average S/N >=5.0, allowing for the detection of absorbers above a rest-frame equivalent width limit of W r >= 0.19 Å for the O VI 1032 Å component. Accounting for random interlopers mimicking an O VI doublet, we derive for the first time a secure lower limit for the redshift number density ΔN/Δz for redshifts z abs >= 2.8. With extensive Monte Carlo simulations, we quantify the losses of absorbers due to blending with the ubiquitous Lyα forest lines and estimate the success rate of retrieving each individual candidate as a function of its redshift, the emission redshift of the quasar, the strength of the absorber, and the measured signal-to-noise ratio (S/N) of the spectrum by modeling typical Lyman forest spectra. These correction factors allow us to derive the "incompleteness and S/N-corrected" redshift number densities of O VI absorbers: ΔN O VI,c /Δzc (2.8 < z < 3.2) = 4.6 ± 0.3, ΔN O VI,c /Δzc (3.2 < z < 3.6) = 6.7 ± 0.8, and ΔN O VI,c /Δzc (3.6 < z < 4.0) = 8.4 ± 2.9. We can place a secure lower limit for the contribution of O VI to the closure mass density at the redshifts probed here: ΩO VI (2.8 < z < 3.2) >= 1.9 × 10-8 h -1. We show that the strong lines we probe account for over 65% of the mass in the O VI absorbers; the weak absorbers, while dominant in line number density, do not contribute significantly to the mass density. Making a conservative assumption about the ionization fraction, {O VI}/{O}, and adopting the Anders & Grevesse solar abundance values, we derive the mean metallicity of the gas probed in our search: ζ(2.8 < z < 3.2) >= 3.6 × 10-4 h, in good agreement with other studies. These results demonstrate that large spectroscopic data sets such as SDSS can play an important role in QSO absorption line studies, in spite of