Crossed-beam universal-detection reactive scattering of radical beams characterized by laser-induced-fluorescence: the case of C2 and CN

Continuous supersonic beams of dicarbon (C2) and cyano (CN) radicals have been generated by a high-pressure radio-frequency discharge beam source starting from dilute mixtures in rare gases of suitable precursor molecules. Their internal quantum state distributions have been characterized by laser-induced-fluorescence (LIF) in a new crossed molecular beam-laser apparatus. These supersonic beams have been used to study the reactive scattering of C2 and CN radicals with unsaturated hydrocarbons. This paper reports here on the C2 and CN radical beam characterization by LIF and on dynamics studies of the reactions CN + C2H2 (acetylene) and CN + CH3CCH (methylacetylene) by the crossed molecular beam scattering technique with universal mass spectrometric detection and time-of-flight analysis. The role of CN rovibrational excitation on the dynamics of the CN + C2H2 reaction is discussed with reference to previous dynamics and kinetics studies. These reactions are of interest in the chemistry of planetary atmospheres (Titan) and the interstellar medium as well as in combustion.

[1]  R. Zare,et al.  Tunable laser fluorescence method for product state analysis. , 1974, Science.

[2]  Nadia Balucani,et al.  Reactive scattering of atoms and radicals , 1995 .

[3]  B. Bussery-Honvault,et al.  Dynamics of the C(1D)+H2 reaction: A comparison of crossed molecular beam experiments with quantum mechanical and quasiclassical trajectory calculations on the first two singlet (11A′ and 11A″) potential energy surfaces , 2010 .

[4]  Ian W. M. Smith,et al.  Reaction kinetics at very low temperatures: laboratory studies and interstellar chemistry. , 2000, Accounts of chemical research.

[5]  R. Zare,et al.  Effect of reagent rotation on product energy disposal in the light atom transfer reaction O(3P)+HCl(v=2,J=1,6,9)→OH(v’,N’)+Cl(2P) , 1991 .

[6]  Nadia Balucani,et al.  Crossed beam reaction of cyano radicals with hydrocarbon molecules. IV. Chemical dynamics of cyanoacetylene (HCCCN; X 1Σ+) formation from reaction of CN(X 2Σ+) with acetylene, C2H2(X 1Σg+) , 2000 .

[7]  Nadia Balucani,et al.  Observation of Nitrogen-Bearing Organic Molecules from Reactions of Nitrogen Atoms with Hydrocarbons: A Crossed Beam Study of N(2D) + Ethylene , 2000 .

[8]  P. Casavecchia Chemical reaction dynamics with molecular beams , 2000 .

[9]  W. B. Miller,et al.  Exchange reactions of alkali atoms with alkali halides: a collision complex mechanism , 1967 .

[10]  S. Leone,et al.  Direct detection of polyynes formation from the reaction of ethynyl radical (C2H) with propyne (CH3–CCH) and allene (CH2CCH2) , 2007 .

[11]  Crossed beam studies of radical-radical reactions: O(3P) + C3H5 (allyl). , 2007, Physical chemistry chemical physics : PCCP.

[12]  R. Kaiser,et al.  The formation of nitriles in hydrocarbon-rich atmospheres of planets and their satellites: laboratory investigations by the crossed molecular beam technique. , 2001, Accounts of chemical research.

[13]  Nadia Balucani,et al.  Crossed beam reaction of cyano radicals with hydrocarbon molecules. III. Chemical dynamics of vinylcyanide (C2H3CN;X 1A′) formation from reaction of CN(X 2Σ+) with ethylene, C2H4(X 1Ag) , 2000 .

[14]  Nadia Balucani,et al.  Magnetic analysis of supersonic beams of atomic oxygen, nitrogen, and chlorine generated from a radi , 1997 .

[15]  Armando D. Estillore,et al.  Dynamics of CN+alkane reactions by crossed-beam dc slice imaging. , 2008, The Journal of chemical physics.

[16]  N. Balucani,et al.  Dynamics of the O(3P) + C2H4 reaction: identification of five primary product channels (vinoxy, acetyl, methyl, methylene, and ketene) and branching ratios by the crossed molecular beam technique with soft electron ionization. , 2005, The journal of physical chemistry. A.

[17]  W. B. Miller,et al.  Molecular Beam Kinetics: Four‐Atom Collision Complexes in Exchange Reactions of CsCl with KCl and KI , 1972 .

[18]  Ian W. M. Smith,et al.  Rate coefficients for removal of CN(X2Σ+,ν=2) from selected rotational levels between Ni=0 and 57 in collisions with N2 and C2H2 , 2003 .

[19]  D. Gee,et al.  A versatile source to produce high-intensity, pulsed supersonic radical beams for crossed-beam experiments: The cyanogen radical CN(X2Σ+) as a case study , 1999 .

[20]  Marzio Rosi,et al.  Crossed-beam and theoretical studies of the S(1D) + C2H2 reaction. , 2009, The journal of physical chemistry. A.

[21]  J. Whitehead Molecular beam studies of free-radical processes: photodissociation, inelastic and reactive collisions , 1996 .

[22]  Nadia Balucani,et al.  Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X 2Σ+), with Unsaturated Hydrocarbons , 2000 .

[23]  Colin Tudge,et al.  Planet , 1999 .

[24]  T. Schmidt,et al.  Oscillator strengths of the Mulliken, Swan, Ballik-Ramsay, Phillips, and d3Pi g<--c 3Sigma u+ systems of C2 calculated by MRCI methods utilizing a biorthogonal transformation of CASSCF orbitals. , 2007, The Journal of chemical physics.

[25]  R. Wayne,et al.  Photochemistry of small molecules , 1979, Nature.

[26]  J. Davenport Editor , 1960 .

[27]  Nadia Balucani,et al.  Experimental and theoretical differential cross sections for the reactions Cl+H2/D2 , 2001 .

[28]  Nadia Balucani,et al.  Crossed molecular beam study of gas phase reactions relevant to the chemistry of planetary atmospheres: The case of C2+C2H2 , 2008 .

[29]  J. D. Mcdonald,et al.  Molecular Beam Reactive Scattering Apparatus with Electron Bombardment Detector , 1969 .

[30]  R. Kaiser,et al.  A crossed beams and ab initio investigation on the formation of cyanodiacetylene in the reaction of cyano radicals with diacetylene. , 2009, The Journal of chemical physics.

[31]  N. Balucani,et al.  Probing the dynamics of polyatomic multichannel elementary reactions by crossed molecular beam experiments with soft electron-ionization mass spectrometric detection. , 2009, Physical chemistry chemical physics : PCCP.

[32]  N. Balucani,et al.  Crossed beam studies of elementary reactions of N and C atoms and CN radicals of importance in combustion. , 2001, Faraday discussions.

[33]  Xueming Yang,et al.  Effect of a single quantum rotational excitation on state-to-state dynamics of the O(1D)+H2-->OH+H reaction. , 2002, Physical review letters.

[34]  Ian W. M. Smith,et al.  Low temperature rate coefficients for the reactions of CN and C2H radicals with allene (CH2CCH2) and methyl acetylene (CH3CCH) , 2001 .

[35]  N. Balucani,et al.  Crossed molecular beam studies of C(3P,1D) and C2(X1Σ+g,a3Πu) reactions with acetylene , 2008 .

[36]  Faraday Discuss , 1985 .

[37]  W. Bian,et al.  Dynamics of the Cl+D2 reaction: a comparison of crossed molecular beam experiments with quasi-classical trajectory calculations on a new ab initio potential energy surface , 2000 .

[38]  Nadia Balucani,et al.  Elementary Reactions and Their Role in Gas-Phase Prebiotic Chemistry , 2009, International journal of molecular sciences.

[39]  R. Zare,et al.  Rovibronic state to rovibronic state reaction dynamics: O(3P)+HCl(v=2,J)→OH(v′,N′)+Cl(2P) , 1987 .

[40]  F. Shokoohi,et al.  Collisional metastability of high rotational states of CN(X2Σ+, = 0)☆ , 1985 .

[41]  R. Kaiser,et al.  A crossed beam and ab initio study of the C2(X1Σg+ /a3∏u) + C2H2(X1Σg+) reactions , 2003 .

[42]  R. Levine,et al.  Molecular Reaction Dynamics and Chemical Reactivity , 1987 .

[43]  N. Balucani,et al.  Experimental and theoretical differential cross sections for the N(2D) + H2 reaction. , 2006, The journal of physical chemistry. A.

[44]  Ian W. M. Smith,et al.  C+C2H2: A Key Reaction in Interstellar Chemistry , 2002 .

[45]  Nadia Balucani,et al.  Cyanomethylene Formation from the Reaction of Excited Nitrogen Atoms with Acetylene: A Crossed Beam and ab Initio Study , 2000 .

[46]  M. Costes,et al.  C2 Radicals in a supersonic molecular beam. Radiative lifetime of the d 3Πg state measured by laser-induced fluorescence , 1988 .

[47]  R. Kaiser,et al.  Chemical dynamics of the formation of the 1,3-butadiynyl radical (C4H(X2Sigma+)) and its isotopomers. , 2006, The journal of physical chemistry. A.

[48]  P. Bernath,et al.  Fourier transform spectroscopy of the Swan (d[SUP]3[/SUP]pi[SUB]g[/SUB] - a[SUP]3[/SUP]pi[SUB]u[/SUB]) system of the jet-cooled C2 molecule , 1994 .

[49]  Marzio Rosi,et al.  Crossed-beam dynamics, low-temperature kinetics, and theoretical studies of the reaction S(1D) + C2H4. , 2009, The journal of physical chemistry. A.

[50]  Paul W. Seakins,et al.  H atom branching ratios from the reactions of CN radicals with C2H2 and C2H4 , 2004 .

[51]  W. Jackson,et al.  Rate constants for CN reactions with hydrocarbons and the product HCN vibrational populations: Examples of heavy–light–heavy abstraction reactions , 1992 .

[52]  I. Smith,et al.  Rate coefficients for reaction and for rotational energy transfer in collisions between CN in selected rotational levels (X 2Sigma+, v=2, N=0, 1, 6, 10, 15, and 20) and C2H2. , 2007, The Journal of chemical physics.

[53]  Bian,et al.  van der waals interactions in the Cl + HD reaction , 1999, Science.

[54]  Nadia Balucani,et al.  Crossed molecular beam reactive scattering: from simple triatomic to multichannel polyatomic reactions , 2006 .

[55]  Ian W. M. Smith,et al.  Rate constants for the reactions of CN with hydrocarbons at low and ultra-low temperatures , 1993 .

[56]  Jay B. Jeffries,et al.  Combined cavity ringdown absorption and laser-induced fluorescence imaging measurements of CN(B-X) and CH(B-X) in low-pressure CH4-O2-N2 and CH4-NO-O2-N2 flames , 2001 .

[57]  Nadia Balucani,et al.  Crossed beam reaction of cyano radicals with hydrocarbon molecules. II. Chemical dynamics of 1-cyano-1-methylallene (CNCH3CCCH2; X 1A′) formation from reaction of CN(X 2Σ+) with dimethylacetylene CH3CCCH3 (X 1A1′) , 1999 .

[58]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[59]  S. Leone,et al.  Isomer-specific product detection of CN radical reactions with ethene and propene by tunable VUV photoionization mass spectrometry. , 2009 .

[60]  S. Sibener,et al.  Development of a supersonic O(3PJ), O(1D2) atomic oxygen nozzle beam source , 1980 .

[61]  B. Bussery-Honvault,et al.  Dynamics of the insertion reaction C(1D)+ H2: A comparison of crossed molecular beam experiments with quasiclassical trajectory and quantum mechanical scattering calculations , 2004 .

[62]  Nadia Balucani,et al.  Formation of Three C4H3N Isomers from the Reaction of CN (X2Σ+) with Allene, H2CCCH2 (X1A1), and Methylacetylene, CH3CCH (X1A1): A Combined Crossed Beam and Ab Initio Study , 2002 .

[63]  Giacinto Scoles,et al.  Atomic and Molecular Beam Methods , 1988 .

[64]  Nadia Balucani,et al.  Crossed beam reaction of the cyano radical, CN(X 2Σ+), with methylacetylene, CH3CCH (X 1A1): Observation of cyanopropyne, CH3CCCN (X 1A1), and cyanoallene, H2CCCHCN (X 1A′) , 1999 .

[65]  Michael J Pilling,et al.  H atom yields from the reactions of CN radicals with C2H2, C2H4, C3H6, trans-2-C4H8, and iso-C4H8. , 2007, The journal of physical chemistry. A.

[66]  N. Balucani,et al.  Crossed beam studies of the reactions of atomic oxygen in the ground 3P and first electronically excited 1D states with hydrogen sulfide. , 2004, The Journal of chemical physics.