Cavity ringdown spectroscopy of 13C2H2 in the 12 900–13 400 cm−1 region

Abstract We have utilized an acetylene gas sample to assess the performance of a newly constructed cavity ringdown laser absorption (CRDS) spectrometer at the Arkansas Center for Laser Applications and Science (ArCLAS). During this assessment process, four overtone combination bands were observed for the 13 C 2 H 2 species, three of which have not been previously reported in the literature. For two of these previously unreported bands, a total of 85 rovibrational transitions (over 40 in each band) have been assigned using ground state combination difference theory. The data have been fit to standard energy expressions, and a set of molecular constants for each overtone combination band have been obtained. Here we present a brief description of the ArCLAS CRDS instrument along with the complete rovibrational analysis of these two combination overtone bands.

[1]  J. V. Auwera,et al.  Vibrational Spectroscopic Database on Acetylene, X̃ 1Σg+ (12C2H2, 12C2D2, and 13C2H2) , 2003 .

[2]  A. Campargue,et al.  High-resolution Fourier-transform intra-cavity laser absorption spectroscopy : Application to 12C2H2 near 12300 cm-1 , 2003 .

[3]  L. Fusina,et al.  High-resolution infrared spectroscopy of H12C13CD and H13C12CD in the 470–5200 cm−1 spectral region , 2007 .

[4]  F. Stoeckel,et al.  Overtone spectroscopy of acetylene near 13 500 cm−1 , 1992 .

[5]  A. Pisarchik,et al.  The Fourier transform spectrum of the coloured vibrations in mono and dideuteroacetylene , 1993 .

[6]  L. Halonen,et al.  High-resolution Fourier-transform intra-cavity laser absorption study of H12C13CH and H13C13CH at around 12600 cm-1: A case of strong anharmonic resonances , 2004 .

[7]  D. Romanini,et al.  Overtone spectroscopy in the blue region by cavity-enhanced absorption spectroscopy with a mode-locked femtosecond laser: application to acetylene , 2004 .

[8]  Brian C. Smith,et al.  The C–H overtone spectra of acetylene: Bend/stretch interactions below 10 000 cm−1 , 1988 .

[9]  B. Henry,et al.  The overtone spectrum of acetylene: A rotational analysis based on a local model description , 1982 .

[10]  Brian C. Smith,et al.  The overtone dynamics of acetylene above 10 000 cm−1 , 1991 .

[11]  M. Herman,et al.  Spectroscopic investigation of vibration–rotation bands in acetaldehyde:: Focus on the nν3 (n=1–5) aldehyde CH stretch bands , 1999 .

[12]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure , 1992 .

[13]  W. D. Watson.  Ion-Molecule Reactions, Molecule Formation, and Hydrogen-Isotope Exchange in Dense Interstellar Clouds , 1974 .

[14]  A. O’Keefe,et al.  Cavity ring‐down optical spectrometer for absorption measurements using pulsed laser sources , 1988 .

[15]  Y. Tamura,et al.  Practical optical frequency measurement system around 1.5 μm based on an acetylene-stabilized laser-locked optical frequency comb , 2007 .

[16]  Michelle L. Silva,et al.  Rovibrational spectroscopy of the v=6 manifold in 12C2H2 and 13C2H2 , 2000 .

[17]  David P. Shoemaker,et al.  Experiments in physical chemistry , 1962 .

[18]  E. Venuti,et al.  Vibration-Rotation Spectra of 13C Containing Acetylene , 1993 .

[19]  D. Hurtmans,et al.  The vibration–rotation spectrum of 12C2HD: new overtone bands and global vibrational analysis , 2004 .

[20]  L. Halonen,et al.  High repetition rate cavity ringdown spectroscopy of vibrational overtones of H13C13CH at around 12 200 cm−1 , 2006 .

[21]  Alan A. Madej,et al.  Development and study of a 1.5 μm optical frequency standard referenced to the P(16) saturated absorption line in the (ν1+ν3) overtone band of 13C2H2 , 2004 .

[22]  A. L. Utz,et al.  Energy transfer in highly vibrationally excited acetylene: Relaxation for vibrational energies from 6500 to 13 000 cm−1 , 1992 .

[23]  Chen,et al.  Chaos and dynamics on 0.5-300 ps time scales in vibrationally excited acetylene: Fourier transform of stimulated-emission pumping spectrum. , 1987, Physical review letters.

[24]  R. Vivie-Riedle,et al.  Design of optimal infrared femtosecond laser pulses for the overtone excitation in acetylene , 2001 .

[25]  A. J. Merer,et al.  Darling-Dennison resonance and Coriolis coupling in the bending overtones of the A 1A(u) state of acetylene, C2H2. , 2008, The Journal of chemical physics.

[26]  Jun Ye,et al.  Ultrasensitive frequency-modulation spectroscopy enhanced by a high-finesse optical cavity: theory and application to overtone transitions of C 2 H 2 and C 2 HD , 1999 .

[27]  L. Halonen,et al.  High-resolution photoacoustic overtone spectrum of acetylene near 570 nm using a ring-dye-laser spectrometer , 1991 .

[28]  Jean Vander Auwera,et al.  Global and accurate vibration Hamiltonians from high resolution molecular spectroscopy , 1999 .

[29]  S. Rosenwaks,et al.  COMBINATION BANDS VERSUS OVERTONE STRETCH EXCITATION AND ROTATIONAL EFFECTS IN VIBRATIONALLY MEDIATED PHOTODISSOCIATION OF ACETYLENE , 1998 .

[30]  Hua Guo,et al.  A scaled ab initio potential energy surface for acetylene and vinylidene , 2003 .

[31]  D. Liotard,et al.  A theoretical study of acetylene: toward the complete characterization of the singlet ground state potential energy surface , 1993 .

[32]  Wing Tsang,et al.  Chemical Kinetic Data Base for Propellant Combustion I. Reactions Involving NO, NO2, HNO, HNO2, HCN and N2O , 1991 .

[33]  K. Lehmann,et al.  Variational calculation of the rotational constants for acetylene and its isotopic derivatives , 1983 .

[34]  L. Giver,et al.  Intensity measurements and rotational intensity distribution for the oxygen A-band , 1969 .

[35]  D. Brenner,et al.  Empirical potential for hydrocarbons for use in simulating the chemical vapor deposition of diamond films. , 1990, Physical review. B, Condensed matter.

[36]  P. Gaspard,et al.  Overtone spectroscopy and dynamics in monodeuteroacetylene (C2HD) , 1995 .

[37]  S. Carter,et al.  Potential models and local mode vibrational eigenvalue calculations for acetylene , 1982 .

[38]  R. Silbey,et al.  Pure bending dynamics in the acetylene X̃ 1Σg+ state up to 15 000 cm−1 of internal energy , 1998 .

[39]  E. Herbst,et al.  Metastable isomers - A new class of interstellar molecules , 1979 .

[40]  S. Gozzini,et al.  Diode laser spectroscopy of ammonia and ethylene overtones. , 2004, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[41]  K. Lehmann,et al.  The high‐resolution visible overtone spectrum of acetylenea) , 1983 .