WorldWideScience

Sample records for cyanoacetylene

  1. Ionization photophysics and spectroscopy of cyanoacetylene

    International Nuclear Information System (INIS)

    Leach, Sydney; Champion, Norbert; Garcia, Gustavo A.; Fray, Nicolas; Gaie-Levrel, François; Mahjoub, Ahmed; Bénilan, Yves; Gazeau, Marie-Claire; Schwell, Martin

    2014-01-01

    Photoionization of cyanoacetylene was studied using synchrotron radiation over the non-dissociative ionization excitation range 11–15.6 eV, with photoelectron-photoion coincidence techniques. The absolute ionization cross-section and spectroscopic aspects of the parent ion were recorded. The adiabatic ionization energy of cyanoacetylene was measured as 11.573 ± 0.010 eV. A detailed analysis of photoelectron spectra of HC 3 N involves new aspects and new assignments of the vibrational components to excitation of the A 2 Σ + and B 2 Π states of the cation. Some of the structured autoionization features observed in the 11.94 to 15.5 eV region of the total ion yield (TIY) spectrum were assigned to two Rydberg series converging to the B 2 Π state of HC 3 N + . A number of the measured TIY features are suggested to be vibrational components of Rydberg series converging to the C 2 Σ + state of HC 3 N + at ≈17.6 eV and others to valence shell transitions of cyanoacetylene in the 11.6–15 eV region. The results of quantum chemical calculations of the cation electronic state geometries, vibrational frequencies and energies, as well as of the C–H dissociation potential energy profiles of the ground and electronic excited states of the ion, are compared with experimental observations. Ionization quantum yields are evaluated and discussed and the problem of adequate calibration of photoionization cross-sections is raised

  2. Ionization photophysics and spectroscopy of cyanoacetylene

    Energy Technology Data Exchange (ETDEWEB)

    Leach, Sydney; Champion, Norbert [LERMA UMR CNRS 8112, Observatoire de Paris-Meudon, 5 place Jules-Jansen, 92195 Meudon (France); Garcia, Gustavo A.; Fray, Nicolas; Gaie-Levrel, François [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, B.P. 48, 91192, Gif-sur-Yvette Cedex (France); Mahjoub, Ahmed; Bénilan, Yves; Gazeau, Marie-Claire; Schwell, Martin [LISA UMR CNRS 7583, Université Paris Est Créteil and Université Paris Diderot, Institut Pierre Simon Laplace, 61 Avenue du Général de Gaulle, 94010 Créteil (France)

    2014-05-07

    Photoionization of cyanoacetylene was studied using synchrotron radiation over the non-dissociative ionization excitation range 11–15.6 eV, with photoelectron-photoion coincidence techniques. The absolute ionization cross-section and spectroscopic aspects of the parent ion were recorded. The adiabatic ionization energy of cyanoacetylene was measured as 11.573 ± 0.010 eV. A detailed analysis of photoelectron spectra of HC{sub 3}N involves new aspects and new assignments of the vibrational components to excitation of the A{sup 2}Σ{sup +} and B{sup 2}Π states of the cation. Some of the structured autoionization features observed in the 11.94 to 15.5 eV region of the total ion yield (TIY) spectrum were assigned to two Rydberg series converging to the B{sup 2}Π state of HC{sub 3}N{sup +}. A number of the measured TIY features are suggested to be vibrational components of Rydberg series converging to the C{sup 2}Σ{sup +} state of HC{sub 3}N{sup +} at ≈17.6 eV and others to valence shell transitions of cyanoacetylene in the 11.6–15 eV region. The results of quantum chemical calculations of the cation electronic state geometries, vibrational frequencies and energies, as well as of the C–H dissociation potential energy profiles of the ground and electronic excited states of the ion, are compared with experimental observations. Ionization quantum yields are evaluated and discussed and the problem of adequate calibration of photoionization cross-sections is raised.

  3. The ν 1Band System of H-CC-CN (Cyanoacetylene)

    Science.gov (United States)

    Winther, F.; Klee, S.; Mellau, G.; Naı̈m, S.; Mbosei, L.; Fayt, A.

    1996-02-01

    The ν1band system of cyanoacetylene (H-CC-CN) has been observed with an effective resolution of 0.006 cm-1. ν1= 3327.37085(3) cm-1,B1= 0.15149762(2) cm-1,D1= 1.8065(3) × 10-8cm-1. Several hot bands from the statesv5= 1,v6= 1,v7= 1, 2 (l= 0 and 2), 3 (l= 1 and 3), and 4 (l= 0 and 2),v6=v7= 1 (l= 0 and 2), andv6= 1 andv7= 2 (l= 3) have also been observed and analyzed. Many bands show strong local perturbations due to interactions with states which are combinations of the modes 4, 5, 6, and 7. These perturbing states are also described quantitatively, and rovibrational constants are given.

  4. A Theoretical Study of the Photodissociation Mechanism of Cyanoacetylene in Its Lowest Singlet and Triplet Excited States

    Science.gov (United States)

    Luo, Cheng; Du, Wei-Na; Duan, Xue-Mei; Li, Ze-Sheng

    2008-11-01

    Cyanoacetylene (H5-C4 ≡ C3-C2 ≡ N1) is a minor constituent of the atmosphere of Titan, and its photochemistry plays an important role in the formation of the haze surrounding the satellite. In this paper, the complete active space self-consistent field (CASSCF) and multiconfigurational second-order perturbation (CASPT2) approaches are employed to investigate the photochemical processes for cyanoacetylene in its first singlet and triplet excited states with the cc-pVTZ basis set. Fissions of the C4-H5 and C2-C3 bonds in S1 yield H(2S) + CCCN(A2Π) and HCC(A2Π) + CN(X2Σ+), respectively. In T1, the corresponding dissociation products are H(2S) + CCCN(X2Σ+) and HCC(X2Σ) + CN(X2Σ+). At the CASPT2(14,13)//CASSCF(14,13) + ZPE level, the barriers for the adiabatic dissociation of the C4-H5 and C2-C3 bonds are 6.11 and 6.94 eV in S1 and 5.71 and 6.39 eV in T1, respectively, taking the energy of S0 minimum as reference. Based on the calculated potential energy surfaces, the existence of a metastable excited molecule is anticipated upon 260-230 nm photoexcitation, which provides a probable approach for cyanoacetylene to polymerize. The internal conversion (IC) process through vibronic interaction followed by C4-H5 fission in the ground state is found to account for the observed diffuse character in the UV absorption spectrum below 240 nm.

  5. An experimental study of the reactivity of CN and C3N anions with cyanoacetylene (HC3N)

    Czech Academy of Sciences Publication Activity Database

    Romanzin, C.; Louarn, E.; Lemaire, J.; Žabka, Ján; Polášek, Miroslav; Guillemin, J.-C.; Alcaraz, Ch.

    2016-01-01

    Roč. 268, APR 2016 (2016), s. 242-252 ISSN 0019-1035 R&D Projects: GA ČR(CZ) GA14-19693S; GA MŠk(CZ) LD14024 Grant - others:COST(XE) CM0805; COST(XE) TD1308 Institutional support: RVO:61388955 Keywords : ionosoheres * titan * satellites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.131, year: 2016

  6. Recent interstellar molecular line work

    International Nuclear Information System (INIS)

    Winnewisser, G.

    1975-01-01

    A summary of recent interstellar molecular line work is presented. Transitions of the following molecules have been detected in Sgr B2: Vinylcyanide, H 2 C 2 HCN, formic acid, HCOOH, dimethyl ether (CH 3 ) 2 O and isotopically labelled cyanoacetylene- 13 C,HC 13 CCN and HCC 13 CN. The data on cyanoacetylene give an upper limit to the abundance ratio 12 C/ 13 C of 36 +- 5. A short discussion of the interstellar chemistry leads to the conclusion that hydrocarbons such as acetylene, HCCH, ethylen, H 2 CCH 2 and ethane H 3 CCH 3 should be present in interstellar clouds. 13 refs

  7. Production and loss of HC3N in interstellar clouds: some relevant laboratory measurements

    International Nuclear Information System (INIS)

    Knight, J.S.; Freeman, C.G.; McEwan, M.J.; Smith, S.C.; Adams, N.G.; Smith, D.

    1986-01-01

    The results of recent selected ion flow tube (SIFT) experiments on the ion-molecule chemistry of cyanoacetylene are considered in the context of the chemistry of HC 3 N in the interstellar environment. Important errors revealed by this SIFT investigation, following an earlier flowing afterglow study in the authors' laboratory, have led to a different perception of the ion-molecule chemistry that HC 3 N may undergo in interstellar clouds. It is now evident that insertion and association occur in the reactions of hydrocarbon ions with HC 3 N. (author)

  8. Interferometric imaging of Titan's HC$_3$N, H$^{13}$CCCN and HCCC$^{15}$N

    OpenAIRE

    Cordiner, M. A.; Nixon, C. A.; Charnley, S. B.; Teanby, N. A.; Molter, E. M.; Kisiel, Z.; Vuitton, V.

    2018-01-01

    We present the first maps of cyanoacetylene isotopologues in Titan's atmosphere, including H$^{13}$CCCN and HCCC$^{15}$N, detected in the 0.9 mm band using the Atacama Large Millimeter/submillimeter array (ALMA) around the time of Titan's (southern winter) solstice in May 2017. The first high-resolution map of HC$_3$N in its $v_7=1$ vibrationally excited state is also presented, revealing a unique snapshot of the global HC$_3$N distribution, free from the strong optical depth effects that adv...

  9. Dipole moments of molecules solvated in helium nanodroplets

    International Nuclear Information System (INIS)

    Stiles, Paul L.; Nauta, Klaas; Miller, Roger E.

    2003-01-01

    Stark spectra are reported for hydrogen cyanide and cyanoacetylene solvated in helium nanodroplets. The goal of this study is to understand the influence of the helium solvent on measurements of the permanent electric dipole moment of a molecule. We find that the dipole moments of the helium solvated molecules, calculated assuming the electric field is the same as in vacuum, are slightly smaller than the well-known gas-phase dipole moments of HCN and HCCCN. A simple elliptical cavity model quantitatively accounts for this difference, which arises from the dipole-induced polarization of the helium

  10. Semiclassical spectral quantization: Application to two and four coupled molecular degrees of freedom

    International Nuclear Information System (INIS)

    De Leon, N.; Heller, E.J.

    1984-01-01

    Semiclassical quantization of the quasiperiodic vibrational motion of molecules is usually based on Einstein--Brillouin--Keller (EBK) conditions for the quantization of the classical actions. Explicit use of the EBK conditions for molecular systems of K degrees of freedom requires K quantization conditions. Therefore, explicit use of the EBK conditions becomes increasingly difficult if not impossible for polyatomic systems of three or more degrees of freedom. In this paper we propose a semiclassical quantization method which makes explicit use of phase coherence of the de Broglie wave associated with the trajectory rather than the EBK conditions. We show that taking advantage of phase coherence reduces the K quantization conditions to a single quantum condition: regardless of the number of degrees of freedom. For reasons that will become obvious we call this method ''spectral quantization.'' Polyatomic vibrational wave functions and energy eigenvalues are generated from quasiperiodic classical trajectories. The spectral method is applied to an ABA linear triatomic molecule with two degrees of freedom and to an anharmonic model of the molecule cyanoacetylene. The usefulness of the technique is demonstrated in this latter calculation since the cyanoacetylene model will have four coupled vibrational degrees of freedom

  11. VUV photoionization and dissociative photoionization of the prebiotic molecule acetyl cyanide: Theory and experiment

    International Nuclear Information System (INIS)

    Bellili, A.; Hochlaf, M.; Schwell, M.; Bénilan, Y.; Fray, N.; Gazeau, M.-C.; Mogren Al-Mogren, M.; Guillemin, J.-C.; Poisson, L.

    2014-01-01

    The present combined theoretical and experimental investigation concerns the single photoionization of gas-phase acetyl cyanide and the fragmentation pathways of the resulting cation. Acetyl cyanide (AC) is inspired from both the chemistry of cyanoacetylene and the Strecker reaction which are thought to be at the origin of medium sized prebiotic molecules in the interstellar medium. AC can be formed by reaction from cyanoacetylene and water but also from acetaldehyde and HCN or the corresponding radicals. In view of the interpretation of vacuum ultraviolet (VUV) experimental data obtained using synchrotron radiation, we explored the ground potential energy surface (PES) of acetyl cyanide and of its cation using standard and recently implemented explicitly correlated methodologies. Our PES covers the regions of tautomerism (between keto and enol forms) and of the lowest fragmentation channels. This allowed us to deduce accurate thermochemical data for this astrobiologically relevant molecule. Unimolecular decomposition of the AC cation turns out to be very complex. The implications for the evolution of prebiotic molecules under VUV irradiation are discussed

  12. VUV photoionization and dissociative photoionization of the prebiotic molecule acetyl cyanide: Theory and experiment

    Energy Technology Data Exchange (ETDEWEB)

    Bellili, A.; Hochlaf, M., E-mail: hochlaf@univ-mlv.fr, E-mail: martin.schwell@lisa.u-pec.fr [Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, Université Paris-Est, 5 bd Descartes, 77454 Marne-la-Vallée (France); Schwell, M., E-mail: hochlaf@univ-mlv.fr, E-mail: martin.schwell@lisa.u-pec.fr; Bénilan, Y.; Fray, N.; Gazeau, M.-C. [Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), UMR 7583 CNRS, Institut Pierre et Simon Laplace, Universités Paris-Est Créteil et Paris Diderot, 61 Avenue du Général de Gaulle, 94010 Créteil (France); Mogren Al-Mogren, M. [Chemistry Department, Faculty of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Guillemin, J.-C. [Institut des Sciences Chimiques de Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Allée de Beaulieu, CS 50837, 35708 Rennes Cedex 7 (France); Poisson, L. [Laboratoire Francis Perrin, CNRS URA 2453, CEA, IRAMIS, Laboratoire Interactions Dynamique et Lasers, Bât 522, F-91191 Gif/Yvette (France)

    2014-10-07

    The present combined theoretical and experimental investigation concerns the single photoionization of gas-phase acetyl cyanide and the fragmentation pathways of the resulting cation. Acetyl cyanide (AC) is inspired from both the chemistry of cyanoacetylene and the Strecker reaction which are thought to be at the origin of medium sized prebiotic molecules in the interstellar medium. AC can be formed by reaction from cyanoacetylene and water but also from acetaldehyde and HCN or the corresponding radicals. In view of the interpretation of vacuum ultraviolet (VUV) experimental data obtained using synchrotron radiation, we explored the ground potential energy surface (PES) of acetyl cyanide and of its cation using standard and recently implemented explicitly correlated methodologies. Our PES covers the regions of tautomerism (between keto and enol forms) and of the lowest fragmentation channels. This allowed us to deduce accurate thermochemical data for this astrobiologically relevant molecule. Unimolecular decomposition of the AC cation turns out to be very complex. The implications for the evolution of prebiotic molecules under VUV irradiation are discussed.

  13. AN INFRARED SPECTROSCOPIC STUDY OF AMORPHOUS AND CRYSTALLINE ICES OF VINYLACETYLENE AND IMPLICATIONS FOR SATURN'S SATELLITE TITAN

    International Nuclear Information System (INIS)

    Kim, Y. S.; Kaiser, R. I.

    2009-01-01

    Laboratory infrared spectra of amorphous and crystalline vinylacetylene ices were recorded in the range of 7000-400 cm -1 . The spectra showed several amorphous features in the ice deposited at 10 K, which were then utilized to monitor a phase transition between 93 ± 1 K to form the crystalline structure. Successive heating allows monitoring of the sublimation profile of the vinylacetylene sample in the range of 101-120 K. Considering Titan's surface temperature of 94 K, vinylacetylene ice is likely to be crystalline. Analogous studies on related planetary-bound molecules such as triaceylene and cyanoacetylene may be further warranted to gain better perspectives into the composition of the condensed phases in the Titan's atmosphere (aerosol particles) and of Titan's surface. Based on our studies, we recommend utilizing the ν 1 and ν 16 //ν 11 /ν 17 fundamentals at about 3300 and 650 cm -1 to determine if solid vinylacetylene is crystalline or amorphous on Titan.

  14. Microwave spectrum, structure, and quantum chemical studies of a compound of potential astrochemical and astrobiological interest: Z-3-amino-2-propenenitrile.

    Science.gov (United States)

    Askeland, Eva; Møllendal, Harald; Uggerud, Einar; Guillemin, Jean-Claude; Aviles Moreno, Juan-Ramon; Demaison, Jean; Huet, Thérèse R

    2006-11-23

    Z-3-Amino-2-propenenitrile, H2NCH=CHCN, a compound of astrochemical and astrobiological interest, has been studied by Stark and Fourier transform microwave spectroscopy along with eight of its isotopologues; the synthesis of five of these are reported. The spectra of the ground vibrational state and of three vibrationally excited states belonging to the two lowest normal modes were assigned for the parent species, whereas the ground states were assigned for the isotopologues. The frequency of the lowest in-plane bending fundamental vibration was determined to be 152(20) cm(-1) and the frequency of the lowest out-of-plane fundamental mode was found to be 176(20) cm(-1) by relative intensity measurements. A delicate problem is whether this compound is planar or slightly nonplanar. It was found that the rotational constants of the nine species cannot be used to conclude definitely whether the molecule is planar or not. The experimental dipole moment is mu(a) = 16.45(12), mu(b) = 2.86(6), mu(c) = 0 (assumed), and mu(tot.) = 16.70(12) x 10(-30) C m [5.01(4) D]. The quadrupole coupling constants of the two nitrogen nuclei are chi(aa) = -1.4917(21) and chi(cc) = 1.5644(24) MHz for the nitrogen atom of the cyano group and chi(aa) = 1.7262(18) and chi(cc) = -4.0591(17) MHz for the nitrogen atom of the amino group. Extensive quantum-chemical calculations have been performed, and the results obtained from these calculations have been compared with the experimental values. The equilibrium structures of vinylamine, vinyl cyanide, and Z-3-amino-2-propenenitrile have been calculated. These calculations have established that the equilibrium structure of the title compound is definitely nonplanar. However, the MP2/VQZ energy difference between the planar and nonplanar forms is small, only -423 J/mol. Z-Amino-2-propenenitrile and E-3-amino-2-propenenitrile are formed simply by mixing ammonia and cyanoacetylene at room temperature. A plausible reaction path has been modeled. G3

  15. Possible Origin for Porphin Derivatives in Prebiotic Chemistry a Computational Study

    Science.gov (United States)

    Aylward, Nigel; Bofinger, Neville

    2005-08-01

    A set of chemical reactions is postulated to account for the formation of the macrocyclic porphin structure, basic to the pyrrole derivatives chlorophyll, protoporphyrin, heme and bilirubin, important in photosynthesis, respiration and digestion. A set of equations is given for the prebiotic synthesis of porphin derivatives from the simple molecules; cyanoacetylene, diacetylene, carbon monoxide and ammonia that have been detected in space. A number of isomers of hydrogenated porphin arise which may lose hydrogen to give ultimately porphin and its dehydrogenated derivative. The reactions, while not unique, provide a pathway which has been shown to be feasible from the overall enthalpy changes in the ZKE approximation at the HF and MP2/6-31G* level

  16. Carbon Chemistry in IRC+10216: Infrared Detection of Diacetylene

    Science.gov (United States)

    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.

  17. Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

    Science.gov (United States)

    Hudson, R. L.; Moore, M. H.

    2004-12-01

    Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH 3CN, CH 3CH 2CN, CH 2CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH 3) 2CHCN and (CH 3) 3CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH 3CN, CH 3CH 2CN, and (CH 3) 2CHCN also formed ketenimines. In the presence of H 2O, no isonitriles were detected but rather the cyanate ion (OCN -) was seen in all cases. Although isonitriles, ketenimines, and OCN - were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.

  18. Research and development of basic technologies for next generation industries, 'electrically conductive polymeric material'. Evaluation on first term research and development; Jisedai sangyo kiban gijutsu kenkyu kaihatsu. Dodensei kobunshi zairyo (daiikki kenkyu kaihatsu hyoka)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1985-03-30

    The research and development in the first term has searched widely different kinds of raw materials, elucidated electricity conduction mechanism, discussed processing technologies and evaluation methods. It also included molecule designing to develop new raw materials. A method for growing good single crystals of charge migrating complexes was developed, and (BEDT-TTF){sub 2}I{sub 3} crystals were found to manifest superconductivity at 8K under pressure of 1.3 kbar. In addition, elucidation was made on conduction characteristics of (TMTSF){sub 2}ClO{sub 4} being an induction superconductor, and on its superconduction mechanism. Polyacetylene films oriented at a high level by epitaxial polymerization were synthesized, the carrier hopping mechanism of polyacetylene was proposed, and the direction of increasing the conductivity was shown. It was discovered that cyanoacetylene is thermally polymerized at a relatively low temperature, turning into polymer with good orientation and easily into graphite. Polymeric intermediates soluble to polyparaphenylene vinylene (PPV) were synthesized, whereas these intermediates were found to have shaping and stretching properties, and conductivity of 2.8 times 10{sup 3}s/cm was obtained in PPV doped after the stretching. (NEDO)

  19. Dipole-bound states as doorways in (dissociative) electron attachment

    International Nuclear Information System (INIS)

    Sommerfeld, Thomas

    2005-01-01

    This communication starts with a comparison of dissociative recombination and dissociative attachment placing emphasis on the role of resonances as reactive intermediates. The main focus is then the mechanism of electron attachment to polar molecules at very low energies (100 meV). The scheme considered consists of two steps: First, an electron is captured in a diffuse dipole-bound state depositing its energy in the vibrational degrees of freedom, in other words, a vibrational Feshbach resonance is formed. Then, owing to the coupling with a valence state, the electron is transferred into a compact valence orbital, and depending on the electron affinities of the valence state and possible dissociation products, as well as on the details of the intramolecular redistribution of vibrational energy, long-lived anions can be generated or dissociation reactions can be initiated. The key property in this context is the electronic coupling strength between the diffuse dipole-bound and the compact valence states. We describe how the coupling strength can be extracted from ab initio data, and present results for Nitromethane, Uracil and Cyanoacetylene

  20. INFRARED SPECTRA AND OPTICAL CONSTANTS OF NITRILE ICES RELEVANT TO TITAN's ATMOSPHERE

    International Nuclear Information System (INIS)

    Moore, Marla H.; Hudson, Reggie; Ferrante, Robert F.; James Moore, W.

    2010-01-01

    Spectra and optical constants of nitrile ices known or suspected to be in Titan's atmosphere are presented from 2.0 to 333.3 μm (∼5000-30 cm -1 ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied are: HCN, hydrogen cyanide; C 2 N 2 , cyanogen; CH 3 CN, acetonitrile; C 2 H 5 CN, propionitrile; and HC 3 N, cyanoacetylene. For each of these molecules, we also report new cryogenic measurements of the real refractive index, n, determined in both the amorphous and crystalline phases at 670 nm. These new values have been incorporated into our optical constant calculations. Spectra were measured and optical constants were calculated for each nitrile at a variety of temperatures, including, but not limited to, 20, 35, 50, 75, 95, and 110 K, in both the amorphous phase and the crystalline phase. This laboratory effort used a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference was used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryostat. Optical constants, real (n) and imaginary (k) refractive indices, were determined using Kramers-Kronig analysis. Our calculation reproduces the complete spectrum, including all interference effects.

  1. Infrared Spectra and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

    Science.gov (United States)

    Anderson, Carrie; Ferrante, Robert F.; Moore, W. James; Hudson, Reggie; Moore, Marla H.

    2011-01-01

    Spectra and optical constants of nitrile ices known or suspected to be in Titan?s atmosphere have been determined from 2.0 to 333.3 microns (approx.5000 to 30/cm). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan?s winter pole. Ices studied were: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C2H5CN, propionitrile; and HC3N, cyanoacetylene. Optical constants were calculated, using Kramers-Kronig analysis, for each nitrile ice?s spectrum measured at a variety of temperatures, in both the amorphous- and crystalline phases. Spectra were also measured for many of the nitriles after quenching at the annealing temperature and compared with those of annealed ices. For each of these molecules we also measured the real component, n, of the refractive index for amorphous and crystalline phases at 670 nm. Several examples of the information contained in these new data sets and their usefulness in modeling Titan?s observed features will be presented (e.g., the broad emission feature at 160/cm; Anderson and Samuelson, 2011).

  2. Infrared Spectra, Index of Refraction, and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

    Science.gov (United States)

    Moore, Marla; Ferrante, Robert; Moore, William; Hudson, Reggie

    2010-01-01

    Spectra and optical constants of nitrite ices known or suspected to be in Titan's atmosphere are presented from 2.5 to 200 microns (4000 to 50 per cm ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied include: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C 2H5CN, propionitrile; and HC3N, cyanoacetylene. For each of these molecules we report new measurements of the index of refraction, n, determined in both the amorphous- and crystallinephase at 670 nm. Spectra were measured and optical constants were calculated for each nitrite at a variety of temperatures including 20, 35, 50, 75, 95, and 110 K, in the amorphous- and crystalline-phase. This laboratory effort uses a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference is used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryostat. Optical constants, real (n) and imaginary (k) refractive indices, are determined using Kramers-Kronig (K-K) analysis. Our calculation reproduces the complete spectrum, including all interference effects. Index of refraction measurements are made in a separate dedicated FTIR spectrometer where interference deposit fringes are measured using two 670 nm lasers at different angles to the ice substrate. A survey of these new measurements will be presented along with a discussion of their validation, errors, and application to Titan data.

  3. VUV spectroscopy and photochemistry of five interstellar and putative prebiotic molecules

    Science.gov (United States)

    Schwell, M.; Gaie-Levrel, F.; Bénilan, Y.; Gazeau, M.-C.; Fray, N.; Saul, G.; Champion, N.; Leach, S.; Guillemin, J.-C.

    2012-02-01

    For many years, our group has been investigating the VUV spectroscopy and photochemistry of molecules of astrophysical (Jochims et al. 2006a,b; Leach et al. 2008; Schwell et al. 2012) and prebiotic interest (Schwell et al. 2006). Polyynes and cyano-polyynes that are abundant in the interstellar medium (ISM) and in planetary atmospheres, have been investigated too (e.g. Fray et al. 2010). An aerosol source for reactive and thermo-labile compounds has been developed (Gaie-Levrel et al. 2011) to perform gas-phase measurements. These are necessary to measure intrinsic molecular properties and to compare to quantum chemical calculations. Besides measuring absolute absorption and photoionization cross sections, dissociative channels and their involved excited states are identified for a number of molecules of interstellar interest. Branching ratios of the respective elementary photoreactions are determined in order to understand and model the photochemistry occurring in the ISM. Some very recent results on the dissociative photoionization of methylformate (MF), glycolaldehyde (GA), dimethylether (DIM), aminoacetonitrile (AAC) and cyanoacetylene (CA), are presented here.

  4. Research and development of basic technologies for next generation industries, 'electrically conductive polymeric material'. Evaluation on first term research and development; Jisedai sangyo kiban gijutsu kenkyu kaihatsu. Dodensei kobunshi zairyo (daiikki kenkyu kaihatsu hyoka)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1985-03-30

    The research and development in the first term has searched widely different kinds of raw materials, elucidated electricity conduction mechanism, discussed processing technologies and evaluation methods. It also included molecule designing to develop new raw materials. A method for growing good single crystals of charge migrating complexes was developed, and (BEDT-TTF){sub 2}I{sub 3} crystals were found to manifest superconductivity at 8K under pressure of 1.3 kbar. In addition, elucidation was made on conduction characteristics of (TMTSF){sub 2}ClO{sub 4} being an induction superconductor, and on its superconduction mechanism. Polyacetylene films oriented at a high level by epitaxial polymerization were synthesized, the carrier hopping mechanism of polyacetylene was proposed, and the direction of increasing the conductivity was shown. It was discovered that cyanoacetylene is thermally polymerized at a relatively low temperature, turning into polymer with good orientation and easily into graphite. Polymeric intermediates soluble to polyparaphenylene vinylene (PPV) were synthesized, whereas these intermediates were found to have shaping and stretching properties, and conductivity of 2.8 times 10{sup 3}s/cm was obtained in PPV doped after the stretching. (NEDO)

  5. Research investigation directed toward extending the useful range of the electromagnetic spectrum

    Science.gov (United States)

    Hartmann, S. R.

    1971-01-01

    The lifetimes and fine structure of He(-) were studied using time-of-flight techniques and quenching by a static axial magnetic field. Using level-crossing spectroscopy the hyperfine constants A and B and the lifetime of the 3 2P3/2 state of Li-7 were measured. Polarization of the Ru 7S level was created as a first step in determining the hyperfine structure of the alkali excited S state. The parametric interaction between light and microwaves in optically pumped Rb-87 vapor were investigated. Measurements and analyses of transitions in formaldehyde and its isotopic species and in the lowest two excited vibrational states of H2CO were also made, as well as of transitions in furan, pyrrole, formic acid, and cyanoacetylene. The Hanle effect was studied in the NO molecule, and RF oscillators were developed with flat, wideband output to observe excited state hyperfine transitions at zero field. Data was generated on the time-dependent behavior of photon echoes in ruby. Stimulated Raman scattering was studied in atomic Tl vapor. A Q switched, temperature-tuned ruby laser was developed which operates between 6934 and 6938 A. The frequency shift due to resonant interaction between identical radiating atoms was calculated.

  6. Behaviour of solid phase ethyl cyanide in simulated conditions of Titan

    Science.gov (United States)

    Couturier-Tamburelli, I.; Toumi, A.; Piétri, N.; Chiavassa, T.

    2018-01-01

    In order to simulate different altitudes in the atmosphere of Titan, we investigated using infrared spectrometry and mass spectrometry the photochemistry of ethyl cyanide (CH3CH2CN) ices at different temperatures. Heating experiments of the solid phase until complete desorption showed up three phase transitions with a first one appearing to be approximately at the temperature of Titan's surface (94 K), measured by the Huygens probe. Ethyl cyanide, whose presence has been suggested in solid phase in Titan, can be considered as another nitrile for photochemical models of the Titan atmosphere after our first study (Toumi et al., 2016) concerning vinyl cyanide (CH2CHCN). The desorption energy of ethyl cyanide has been calculated to be 36.75 ( ± 0.55) kJ mol-1 using IRTF and mass spectroscopical techniques. High energetic photolysis (λ > 120 nm) have been performed and we identified ethyl isocyanide, vinyl cyanide, cyanoacetylene, ethylene, acetylene, cyanhydric acid and a methylketenimine form as photoproducts from ethyl cyanide. The branching ratios of the primary products were determined at characteristic temperatures of Titan thanks to the value of the νCN stretching band strength of ethyl cyanide that has been calculated to be 4.12 × 10-18 cm molecule-1. We also report here for the first time the values of the photodissociation cross sections of C2H5CN for different temperatures.

  7. Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X2Σ+), with Unsaturated Hydrocarbons

    Science.gov (United States)

    Balucani, N.; Asvany, O.; Huang, L. C. L.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.; Bettinger, H. F.

    2000-12-01

    Crossed molecular beam experiments of cyano radicals, CN(X2Σ+, ν=0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X1Σ+g), ethylene, C2H4(X1Ag), methylacetylene, CH3CCH(X1A1), allene, H2CCCH2(X1A1), dimethylacetylene, CH3CCCH3(X1A1'), and benzene, C6H6 (X1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X1Σ+), vinylcyanide, C2H3CN (X1A'), 1-methylcyanoacetylene, CH3CCCN (X1A1), cyanoallene, H2CCCH(CN) (X1A'), 3-methylcyanoacetylene, HCCCH2CN(X1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X1A'), and cyanobenzene, C6H5CN (X1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X1Σ+), and vinylcyanide, C2H3CN (X1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed

  8. Observations of CO in Titan's Atmosphere Using ALMA

    Science.gov (United States)

    Serigano, Joseph; Nixon, Conor A.; Cordiner, Martin; Irwin, Patrick G. J.; Teanby, Nicholas; Charnley, Steven B.; Lindberg, Johan E.; Remijan, Anthony J.

    2015-11-01

    The advent of the Atacama Large Millimeter/submillimeter Array (ALMA) has provided a powerful facility for probing the atmospheres of solar system targets at long wavelengths (84-720 GHz) where the rotational lines of small, polar molecules are prominent. In the dense, nitrogen-dominated atmosphere of Titan, photodissociation of molecular nitrogen and methane leads to a wealth of complex hydrocarbons and nitriles in small abundances. Past millimeter/submillimeter observations, including ground-based observations as well as those by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft, have proven the significance of this wavelength region for the derivation of vertical mixing profiles, latitudinal and seasonal variations, and molecular detections. Previous ALMA studies of Titan have presented mapping and vertical column densities of hydrogen isocyanide (HNC) and cyanoacetylene (HC3N) (Cordiner et al. 2014) as well as the first spectroscopic detection of ethyl cyanide (C2H5CN) in Titan’s atmosphere (Cordiner et al. 2015).Here, we report several submillimetric observations of carbon monoxide (CO) and its isotopologues 13CO, C18O, and C17O in Titan’s atmosphere obtained with flux calibration data from the ALMA Science Archive. We employ NEMESIS, a line-by-line radiative transfer code, to determine the stratospheric abundances of these molecules. The abundance of CO in Titan's atmosphere is determined to be approximately 50±1 ppm, constant with altitude, and isotopic ratios are determined to be approximately 12C/13C = 90, 16O/18O = 470, and 16O/17O = 2800. This report presents the first spectroscopic detection of C17O in the outer solar system, detected at >11σ confidence. This talk will focus on isotopic ratios in CO in Titan's atmosphere and will compare our results to previously measured values for Titan and other bodies in the Solar System. General implications for the history of Titan from measurements of CO and its isotopologues will be

  9. Observed ices in the Solar System

    Science.gov (United States)

    Clark, Roger N.; Grundy, Will; Carlson, Robert R.; Noll, Keith; Gudipati, Murthy; Castillo-Rogez, Julie C.

    2013-01-01

    Ices have been detected and mapped on the Earth and all planets and/or their satellites further from the sun. Water ice is the most common frozen volatile observed and is also unambiguously detected or inferred in every planet and/or their moon(s) except Venus. Carbon dioxide is also extensively found in all systems beyond the Earth except Pluto although it sometimes appears to be trapped rather than as an ice on some objects. The largest deposits of carbon dioxide ice is on Mars. Sulfur dioxide ice is found in the Jupiter system. Nitrogen and methane ices are common beyond the Uranian system. Saturn’s moon Titan probably has the most complex active chemistry involving ices, with benzene (C6H6) and many tentative or inferred compounds including ices of Cyanoacetylene (HC3N), Toluene (C7H8), Cyanogen (C2N2), Acetonitrile (CH3CN), H2O, CO2, and NH3. Confirming compounds on Titan is hampered by its thick smoggy atmosphere. Ammonia was predicted on many icy moons but is notably absent among the definitively detected ices with the possible exception of Enceladus. Comets, storehouses of many compounds that could exist as ices in their nuclei, have only had small amounts of water ice definitively detected on their surfaces. Only one asteroid has had a direct detection of surface water ice, although its presence can be inferred in others. This chapter reviews some of the properties of ices that lead to their detection, and surveys the ices that have been observed on solid surfaces throughout the Solar System.

  10. Low temperature measurement of the vapor pressures of planetary molecules

    Science.gov (United States)

    Kraus, George F.

    1989-01-01

    Interpretation of planetary observations and proper modeling of planetary atmospheres are critically upon accurate laboratory data for the chemical and physical properties of the constitutes of the atmospheres. It is important that these data are taken over the appropriate range of parameters such as temperature, pressure, and composition. Availability of accurate, laboratory data for vapor pressures and equilibrium constants of condensed species at low temperatures is essential for photochemical and cloud models of the atmospheres of the outer planets. In the absence of such data, modelers have no choice but to assume values based on an educated guess. In those cases where higher temperature data are available, a standard procedure is to extrapolate these points to the lower temperatures using the Clausius-Clapeyron equation. Last summer the vapor pressures of acetylene (C2H2) hydrogen cyanide (HCN), and cyanoacetylene (HC3N) was measured using two different methods. At the higher temperatures 1 torr and 10 torr capacitance manometers were used. To measure very low pressures, a technique was used which is based on the infrared absorption of thin film (TFIR). This summer the vapor pressure of acetylene was measured the TFIR method. The vapor pressure of hydrogen sulfide (H2S) was measured using capacitance manometers. Results for H2O agree with literature data over the common range of temperature. At the lower temperatures the data lie slightly below the values predicted by extrapolation of the Clausius-Clapeyron equation. Thin film infrared (TFIR) data for acetylene lie significantly below the values predicted by extrapolation. It is hoped to bridge the gap between the low end of the CM data and the upper end of the TFIR data in the future using a new spinning rotor gauge.

  11. Monstrous Ice Cloud System in Titan's Present South Polar Stratosphere

    Science.gov (United States)

    Anderson, Carrie; Samuelson, Robert; McLain, Jason; Achterberg, Richard; Flasar, F. Michael; Milam, Stefanie

    2015-11-01

    During southern autumn when sunlight was still available, Cassini's Imaging Science Subsystem discovered a cloud around 300 km near Titan's south pole (West, R. A. et al., AAS/DPS Abstracts, 45, #305.03, 2013); the cloud was later determined by Cassini's Visible and InfraRed Mapping Spectrometer to contain HCN ice (de Kok et al., Nature, 514, pp 65-67, 2014). This cloud has proven to be only the tip of an extensive ice cloud system contained in Titan's south polar stratosphere, as seen through the night-vision goggles of Cassini's Composite InfraRed Spectrometer (CIRS). As the sun sets and the gloom of southern winter approaches, evidence is beginning to accumulate from CIRS far-IR spectra that a massive system of nitrile ice clouds is developing in Titan's south polar stratosphere. Even during the depths of northern winter, nothing like the strength of this southern system was evident in corresponding north polar regions.From the long slant paths that are available from limb-viewing CIRS far-IR spectra, we have the first definitive detection of the ν6 band of cyanoacetylene (HC3N) ice in Titan’s south polar stratosphere. In addition, we also see a strong blend of nitrile ice lattice vibration features around 160 cm-1. From these data we are able to derive ice abundances. The most prominent (and still chemically unidentified) ice emission feature, the Haystack, (at 220 cm-1) is also observed. We establish the vertical distributions of the ice cloud systems associated with both the 160 cm-1 feature and the Haystack. The ultimate aim is to refine the physical and possibly the chemical relationships between the two. Transmittance thin film spectra of nitrile ice mixtures obtained in our Spectroscopy for Planetary ICes Environments (SPICE) laboratory are used to support these analyses.

  12. Study of irradiation of flash lightning type in a Titan simulated atmosphere

    International Nuclear Information System (INIS)

    Rosa C, J.G. De la

    2001-01-01

    Titan is the greatest satellite of the Saturn planet and the unique moon of the Solar System which presents a dense atmosphere constituted by nitrogen, methane and traces of hydrocarbons and nitriles. Constantly it is bombarded by different energy sources which interacting with the atmosphere cause countless of chemical reactions which have giving origin to the synthesis of organic molecules from its formation since 4.5 thousand millions of years ago. The electric activity was not detected in the satellite when the space probe Voyager I had its nearest match with Titan in November 1980, however, due to the presence of methane clouds rain and of convective activity in the troposphere of the satellite, it is thought in the possible existence of electrical activity in this. In this work it is studied the production of gaseous compounds generated by irradiations type flash lightning in the Titan simulated atmosphere constituted by nitrogen and methane. The lightning are imitated by laser induced plasma (LIP) with similar physical properties to the naturals produced in the Earth. The separation and identification of the organic compounds generated by simulated lightning s were carried out by attached methods of analysis such as the Gas chromatography, Infrared spectroscopy with Fourier transform (FTIR-S) and Mass spectroscopy (MS). The compounds which were identified are: hydrocarbons and nitriles, some of them already have been identified in Titan as well as the hydrogen cyanide (HCN), acetylene, etilene and cyanoacetylene. Moreover we studied the influence that different parameters of irradiation have in the production of organic molecules generated submitting to discharges type lightning the simulated atmosphere of Titan. It was realized an estimation of the available energy in the satellite which could be vanished as discharges type lightning. By means of a model based on conditions of thermodynamic equilibria it was calculated the temperature to which are freeze

  13. Study of irradiation of flash lightning type in a Titan simulated atmosphere; Estudio de irradiaciones tipo relampago en una atmosfera simulada de Titan

    Energy Technology Data Exchange (ETDEWEB)

    Rosa C, J.G. De la

    2001-07-01

    Titan is the greatest satellite of the Saturn planet and the unique moon of the Solar System which presents a dense atmosphere constituted by nitrogen, methane and traces of hydrocarbons and nitriles. Constantly it is bombarded by different energy sources which interacting with the atmosphere cause countless of chemical reactions which have giving origin to the synthesis of organic molecules from its formation since 4.5 thousand millions of years ago. The electric activity was not detected in the satellite when the space probe Voyager I had its nearest match with Titan in November 1980, however, due to the presence of methane clouds rain and of convective activity in the troposphere of the satellite, it is thought in the possible existence of electrical activity in this. In this work it is studied the production of gaseous compounds generated by irradiations type flash lightning in the Titan simulated atmosphere constituted by nitrogen and methane. The lightning are imitated by laser induced plasma (LIP) with similar physical properties to the naturals produced in the Earth. The separation and identification of the organic compounds generated by simulated lightning s were carried out by attached methods of analysis such as the Gas chromatography, Infrared spectroscopy with Fourier transform (FTIR-S) and Mass spectroscopy (MS). The compounds which were identified are: hydrocarbons and nitriles, some of them already have been identified in Titan as well as the hydrogen cyanide (HCN), acetylene, etilene and cyanoacetylene. Moreover we studied the influence that different parameters of irradiation have in the production of organic molecules generated submitting to discharges type lightning the simulated atmosphere of Titan. It was realized an estimation of the available energy in the satellite which could be vanished as discharges type lightning. By means of a model based on conditions of thermodynamic equilibria it was calculated the temperature to which are freeze

  14. The complexity of Orion: an ALMA view. I. Data and first results

    Science.gov (United States)

    Pagani, L.; Favre, C.; Goldsmith, P. F.; Bergin, E. A.; Snell, R.; Melnick, G.

    2017-07-01

    Context. We wish to improve our understanding of the Orion central star formation region (Orion-KL) and disentangle its complexity. Aims: We collected data with ALMA during cycle 2 in 16 GHz of total bandwidth spread between 215.1 and 252.0 GHz with a typical sensitivity of 5 mJy/beam (2.3 mJy/beam from 233.4 to 234.4 GHz) and a typical beam size of 1.̋7 × 1.̋0 (average position angle of 89°). We produced a continuum map and studied the emission lines in nine remarkable infrared spots in the region including the hot core and the compact ridge, plus the recently discovered ethylene glycol peak. Methods: We present the data, and report the detection of several species not previously seen in Orion, including n- and I-propyl cyanide (C3H7CN), and the tentative detection of a number of other species including glycolaldehyde (CH2(OH)CHO). The first detections of gGg' ethylene glycol (gGg' (CH2OH)2) and of acetic acid (CH3COOH) in Orion are presented in a companion paper. We also report the possible detection of several vibrationally excited states of cyanoacetylene (HC3N), and of its 13C isotopologues. We were not able to detect the 16O18O line predicted by our detection of O2 with Herschel, due to blending with a nearby line of vibrationally excited ethyl cyanide. We do not confirm the tentative detection of hexatriynyl (C6H) and cyanohexatriyne (HC7N) reported previously, or of hydrogen peroxide (H2O2) emission. Results: We report a complex velocity structure only partially revealed before. Components as extreme as -7 and +19 km s-1 are detected inside the hot region. Thanks to different opacities of various velocity components, in some cases we can position these components along the line of sight. We propose that the systematically redshifted and blueshifted wings of several species observed in the northern part of the region are linked to the explosion that occurred 500 yr ago. The compact ridge, noticeably farther south displays extremely narrow lines ( 1 km s

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

    Science.gov (United States)

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

    2013-11-01

    isotopologues of vinyl cyanide, cyanoacetylene, and hydrogen cyanide. We also report the detection of transitions from within twelve new vibrationally or torsionally excited states of known molecules. Absorption features produced by diffuse clouds along the line of sight are detected in transitions with low rotation quantum numbers of many simple molecules and are modeled with ~30-40 velocity components with typical linewidths of ~3-5 km s-1. Conclusions: Although the large number of unidentified lines may still allow future identification of new molecules, we expect most of these lines to belong to vibrationally or torsionally excited states or to rare isotopologues of known molecules for which spectroscopic predictions are currently missing. Significant progress in extending the inventory of complex organic molecules in Sgr B2(N) and deriving tighter constraints on their location, origin, and abundance is expected in the near future thanks to an ongoing spectral line survey at 3 mm with ALMA in its cycles 0 and 1. The present single-dish survey will serve as a solid basis for the line identification and analysis of such an interferometric survey. Based on observations carried out with the IRAM 30 m telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).Figures 2-7 and Tables 6-107 are available in electronic form at http://www.aanda.orgThe observed and synthetic 3 mm spectra of Sgr B2(N) and (M), as well as the lists of line identifications corresponding to the blue lab- els in Figs. 2-7, are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/559/A47