One-color (212–220 nm) resonantly-enhanced (S1–S0) multi-photon dissociation of acetylene

Jiang, Jun; Muthike, Angelar K.; Erickson, Trevor J.; Field, Robert W.

doi:10.1016/j.jms.2019.05.006

Title: One-color (212–220 nm) resonantly-enhanced (S₁–S₀) multi-photon dissociation of acetylene

Journal Article · Wed May 22 00:00:00 EDT 2019 · Journal of Molecular Spectroscopy

DOI:https://doi.org/10.1016/j.jms.2019.05.006· OSTI ID:1597427

Jiang, Jun ^[1]; Muthike, Angelar K. ^[2]; Erickson, Trevor J. ^[1]; Field, Robert W. ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Univ. of Michigan, Ann Arbor, MI (United States)

One-color (212–220 nm) multi-photon dissociation of acetylene, resonantly enhanced at the one-photon level by the acetylene S₁–S₀ transition, offers rise to strong photofragment fluorescence signals in the visible and near UV regions. The photofragment fluorescence detection scheme has been applied to obtain rotationally-resolved action-spectra of predissociated S₁ acetylene levels near 47,000 cm^-1. Here, fluorescence signals from the photofragments, generated via individual intermediate S₁ rovibrational levels, are studied in detail, in both flowing gas cell and supersonic jet conditions. In the flow cell setup ( $~$ 1 Torr), dispersed fluorescence (DF) spectra of the photofragments are obtained. For all three S₁ levels used in the DF experiment (rotational levels of the trans $3^{4}, trans$ $3^{5}$ , and cis $3^{1} 6^{1}$ vibrational states), we observe C₂ Swan band ( $d^{3} Π_{g} - a^{3} Π_{u}$ ) and C₂ Deslandres-d’Azambuja band ( $C^{1} Π_{g} - A^{1} Π_{u}$ ) emissions. In the supersonic jet setup (collision-free), fluorescence time-traces at selected wavelength regions are analyzed. In addition to the two C₂ emission bands, we observe a long-lived ( $>$ 3 $μ$ s) visible fluorescence signal, which is likely due to emission from C₂H fragments. Based on our analysis of the DF spectra and the fluorescence time-traces obtained in the supersonic jet apparatus, we propose that the long-lived C₂H species is generated by one-photon photodissociation of S₁ acetylene, and an additional photon photolyzes the C₂H fragment into the C₂ C and d states.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE

Grant/Contract Number:: FG02-87ER13671

OSTI ID:: 1597427

Alternate ID(s):: OSTI ID: 1831794

Journal Information:: Journal of Molecular Spectroscopy, Vol. 361, Issue C; ISSN 0022-2852

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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References (54)

Photodissociation of acetylene: Determination of D ⁰ ₀ (HCC–H) by photofragment imaging Baldwin, David P.; Buntine, Mark A.; Chandler, David W. The Journal of Chemical Physics, Vol. 93, Issue 9 https://doi.org/10.1063/1.458973	journal	November 1990
The Swan System of C ₂ : A Global Analysis of Fourier Transform Emission Spectra Tanabashi, A.; Hirao, T.; Amano, T. The Astrophysical Journal Supplement Series, Vol. 169, Issue 2 https://doi.org/10.1086/510742	journal	April 2007
193 nm photodissociation of acetylene Balko, B. A.; Zhang, J.; Lee, Y. T. The Journal of Chemical Physics, Vol. 94, Issue 12 https://doi.org/10.1063/1.460130	journal	June 1991
Reduced dimension rovibrational variational calculations of the S ₁ state of C ₂ H ₂ . II. The S ₁ rovibrational manifold and the effects of isomerization Changala, P. Bryan; Baraban, Joshua H.; Stanton, John F. The Journal of Chemical Physics, Vol. 140, Issue 2 https://doi.org/10.1063/1.4859876	journal	January 2014
Reduced dimension rovibrational variational calculations of the S ₁ state of C ₂ H ₂ . I. Methodology and implementation Changala, P. Bryan The Journal of Chemical Physics, Vol. 140, Issue 2 https://doi.org/10.1063/1.4859875	journal	January 2014
A New Band System of the C_{2} Molecule. Phillips, John G. The Astrophysical Journal, Vol. 107 https://doi.org/10.1086/145023	journal	March 1948
Lifetime measurements on electronically excited C2(A1Πu) and C2(d3Πg) by laser-induced fluorescence Bauer, W.; Becker, K. H.; Bielefeld, M. Chemical Physics Letters, Vol. 123, Issue 1-2 https://doi.org/10.1016/0009-2614(86)87008-7	journal	January 1986
An Extension of the Phillips System of C_{2} and a Survey of C_{2} States. Ballik, E. A.; Ramsay, D. A. The Astrophysical Journal, Vol. 137 https://doi.org/10.1086/147486	journal	January 1963
Probing the predissociated levels of the S ₁ state of acetylene via H-atom fluorescence and photofragment fluorescence action spectroscopy Jiang, Jun; Saladrigas, Catherine A.; Erickson, Trevor J. The Journal of Chemical Physics, Vol. 149, Issue 17 https://doi.org/10.1063/1.5045046	journal	November 2018
TAIL BANDS OF THE DESLANDRES-D'AZAMBUJA SYSTEM OF THE C ₂ MOLECULE Herzberg, G.; Sutton, R. B. Canadian Journal of Research, Vol. 18a, Issue 4 https://doi.org/10.1139/cjr40a-005	journal	April 1940
Franck-Condon factors based on RKR potentials with applications to radiative absorption coefficients Spindler, Robert J. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 5, Issue 1 https://doi.org/10.1016/0022-4073(65)90039-7	journal	January 1965
Ab initio MO studies on the photodissociation of C2H2 from the S1(1Au) state. II. Mechanism involving triplet states Cui, Qiang; Morokuma, Keiji Chemical Physics Letters, Vol. 272, Issue 5-6 https://doi.org/10.1016/S0009-2614(97)00530-7	journal	July 1997
Ein neues c′1Πg — b1IIu-Bandensystem des C2-Moleküls Messerle, G.; Krauss, L. Zeitschrift für Naturforschung A, Vol. 22, Issue 12 https://doi.org/10.1515/zna-1967-1225	journal	December 1967
Fluorescence of excited ethynyl radicals produced by pulsed vacuum ultraviolet photolyses of C ₂ H ₂ , C ₂ D ₂ , and C ₂ HBr Saito, Y.; Hikida, T.; Ichimura, T. The Journal of Chemical Physics, Vol. 80, Issue 1 https://doi.org/10.1063/1.446448	journal	January 1984
Ab initio molecular orbital studies on the structure, energies, and photodissociation of the electronic excited states of C2H Cui, Qiang; Morokuma, Keiji The Journal of Chemical Physics, Vol. 108, Issue 2 https://doi.org/10.1063/1.475424	journal	January 1998
Ab initio characterization of the state of the acetylene molecule Lievin, Jacques Journal of Molecular Spectroscopy, Vol. 156, Issue 1 https://doi.org/10.1016/0022-2852(92)90098-9	journal	November 1992
Calculated potential surfaces for the description of the emission spectrum of the C2H radical Shih, Shing-Kuo; Peyerimhoff, Sigrid D.; Buenker, Robert J. Journal of Molecular Spectroscopy, Vol. 74, Issue 1 https://doi.org/10.1016/0022-2852(79)90026-2	journal	January 1979
Fluorescence lifetimes and predissociation processes in the B̃ 2A′ state of CCH Chiang, Whe-Yi; Hsu, Yen-Chu The Journal of Chemical Physics, Vol. 112, Issue 17 https://doi.org/10.1063/1.481339	journal	May 2000
Multiphoton vacuum ultraviolet laser dissociation of CH3Br — analysis of chemiluminescent products Baronavski, A. P.; McDonald, J. R. Chemical Physics Letters, Vol. 56, Issue 2 https://doi.org/10.1016/0009-2614(78)80262-0	journal	June 1978
PGOPHER: A program for simulating rotational, vibrational and electronic spectra Western, Colin M. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 186 https://doi.org/10.1016/j.jqsrt.2016.04.010	journal	January 2017
Stretch-bend combination polyads in the Ã1Au state of acetylene, C2H2 Steeves, Adam H.; Bechtel, Hans A.; Merer, Anthony J. Journal of Molecular Spectroscopy, Vol. 256, Issue 2 https://doi.org/10.1016/j.jms.2009.05.005	journal	August 2009
Anharmonic force fields of cis - and trans -S ₁ C ₂ H ₂ Baraban, J. H.; Stanton, J. F.; Merer, A. J. Molecular Physics, Vol. 110, Issue 21-22 https://doi.org/10.1080/00268976.2012.706328	journal	July 2012
The Ã ¹ A _u state of acetylene: ungerade vibrational levels in the region 45,800–46,550 cm ⁻¹ Baraban, Joshua H.; Changala, P. Bryan; Merer, Anthony J. Molecular Physics, Vol. 110, Issue 21-22 https://doi.org/10.1080/00268976.2012.706329	journal	July 2012
Laser photolysis of C2H2 and CF3C2H at 193 nm: Production of C2(d3Πg and CH(A2Δ) and their quenching by Xe Okabe, Hideo; Cody, R. J.; Allen, J. E. Chemical Physics, Vol. 92, Issue 1 https://doi.org/10.1016/0301-0104(85)80006-9	journal	January 1985
Ab initio MO studies on the photodissociation of C2H2 from the S1 (1Au) state. Non-adiabatic effects and S-T interaction Cui, Qiang; Morokuma, Keiji; Stanton, John F. Chemical Physics Letters, Vol. 263, Issue 1-2 https://doi.org/10.1016/S0009-2614(96)01190-6	journal	December 1996
Observation of the LIF spectra of C2(a 3Πu) and C2(A 1Πu) from the photolysis of C2H2 at 193 nm Urdahl, R. S.; Bao, Yihan; Jackson, William M. Chemical Physics Letters, Vol. 152, Issue 6 https://doi.org/10.1016/0009-2614(88)80446-9	journal	November 1988
Rotationally resolved ultraviolet–ultraviolet double resonance study of the nonplanar Ẽ state of acetylene Lundberg, James K.; Jonas, David M.; Rajaram, Bhavani The Journal of Chemical Physics, Vol. 97, Issue 10 https://doi.org/10.1063/1.463543	journal	November 1992
Analysis of Low-Lying Gerade Rydberg States of Acetylene Using Two-Photon Resonance Fluorescence Excitation Spectroscopy Tsuji, Kazuhide; Misawa, Kentaro; Awamura, Junichi The Journal of Physical Chemistry A, Vol. 117, Issue 7 https://doi.org/10.1021/jp308406r	journal	February 2013
Pressure-induced rotational energy transfer in H2CO : Dipolar M-dependence with no single-collision elastic contribution Coy, Stephen L.; Halle, Scott D.; Kinsey, James L. Journal of Molecular Spectroscopy, Vol. 153, Issue 1-2 https://doi.org/10.1016/0022-2852(92)90482-4	journal	May 1992
Cis-trans isomerization in the S ₁ state of acetylene: Identification of cis-well vibrational levels Merer, Anthony J.; Steeves, Adam H.; Baraban, Joshua H. The Journal of Chemical Physics, Vol. 134, Issue 24 https://doi.org/10.1063/1.3599091	journal	June 2011
Near ultraviolet photolysis of C ₂ H ₂ : A precise determination of D ₀ (HCC−H) Mordaunt, David H.; Ashfold, Michael N. R. The Journal of Chemical Physics, Vol. 101, Issue 3 https://doi.org/10.1063/1.467635	journal	August 1994
Spectroscopic characterization of isomerization transition states Baraban, J. H.; Changala, P. B.; Mellau, G. C. Science, Vol. 350, Issue 6266 https://doi.org/10.1126/science.aac9668	journal	December 2015
Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies Changala, P. Bryan; Baraban, Joshua H.; Merer, Anthony J. The Journal of Chemical Physics, Vol. 143, Issue 8 https://doi.org/10.1063/1.4929588	journal	August 2015
C2 Radicals in a supersonic molecular beam. Radiative lifetime of the d 3Πg state measured by laser-induced fluorescence Naulin, C.; Costes, M.; Dorthe, G. Chemical Physics Letters, Vol. 143, Issue 5 https://doi.org/10.1016/0009-2614(88)87402-5	journal	January 1988
High Resolution Lifetime Studies of the d ³ Π _g , C ¹ Π _g and D ¹ Σ _u ⁺ States in C ₂ with Applications to Estimates of the Solar Carbon Abundance Curtis, L.; Engman, B.; Erman, P. Physica Scripta, Vol. 13, Issue 5 https://doi.org/10.1088/0031-8949/13/5/003	journal	May 1976
Revisiting Mulliken’s Concepts about Rydberg States and Rydberg−Valence Interactions from Large-Scale Ab Initio Calculations on the Acetylene Molecule ^† Laruelle, Fabrice; Boyé-Péronne, Séverine; Gauyacq, Dolores The Journal of Physical Chemistry A, Vol. 113, Issue 47 https://doi.org/10.1021/jp903948k	journal	November 2009
Reduced dimension discrete variable representation study of cis–trans isomerization in the S ₁ state of C ₂ H ₂ Baraban, J. H.; Beck, A. R.; Steeves, A. H. The Journal of Chemical Physics, Vol. 134, Issue 24 https://doi.org/10.1063/1.3570823	journal	June 2011
On the Identification of the 3670 A Band of the C_{2} Molecule. Phillips, John G. The Astrophysical Journal, Vol. 112 https://doi.org/10.1086/145322	journal	July 1950
Photochemistry of acetylene Okabe, H. Canadian Journal of Chemistry, Vol. 61, Issue 5 https://doi.org/10.1139/v83-153	journal	May 1983
Photodissociation of C2H at 193 nm: Branching ratios for the formation of C2 in the X 1Σg+, A 1Πu, and B′ 1Σg+ states Sorkhabi, Osman; Blunt, Victor M.; Lin, Hua The Journal of Chemical Physics, Vol. 107, Issue 23 https://doi.org/10.1063/1.475281	journal	December 1997
Fluorescence from photoexcitation of C ₂ H ₂ at 50–106 nm Han, J. C.; Ye, Chao; Suto, Masako The Journal of Chemical Physics, Vol. 90, Issue 8 https://doi.org/10.1063/1.455810	journal	April 1989
Visible emission from the vibrationally hot C2H radical following vacuum-ultraviolet photolysis of acetylene: Experiment and theory Boyé, S.; Campos, A.; Douin, S. The Journal of Chemical Physics, Vol. 116, Issue 20 https://doi.org/10.1063/1.1471239	journal	May 2002
G e r a d e Rydberg states of acetylene studied by multiphoton ionization and photoelectron spectroscopy Ashfold, M. N. R.; Tutcher, B.; Yang, B. The Journal of Chemical Physics, Vol. 87, Issue 9 https://doi.org/10.1063/1.453678	journal	November 1987
Spectroscopy and Predissociation of Acetylene in the np Gerade Rydberg States Tsuji, Kazuhide; Arakawa, Naoko; Kawai, Akio The Journal of Physical Chemistry A, Vol. 106, Issue 5 https://doi.org/10.1021/jp015508i	journal	February 2002
Photodissociation of acetylene and bromoacetylene in the vacuum ultraviolet: Production of electronically excited C ₂ H and C ₂ Okabe, H. The Journal of Chemical Physics, Vol. 62, Issue 7 https://doi.org/10.1063/1.430813	journal	April 1975
Photodissociation of acetylene at 193.3 nm Wodtke, Alec M.; Lee, Y. T. The Journal of Physical Chemistry, Vol. 89, Issue 22 https://doi.org/10.1021/j100268a019	journal	October 1985
Multiphoton-vacuum-ultraviolet laser photodissociation of acetylene: Emission from electronically excited fragments McDonald, J. R.; Baronavski, A. P.; Donnelly, V. M. Chemical Physics, Vol. 33, Issue 2 https://doi.org/10.1016/0301-0104(78)87125-0	journal	September 1978
Vacuum‐Ultraviolet Photolysis of Acetylene Stief, L. J.; DeCarlo, V. J.; Mataloni, R. J. The Journal of Chemical Physics, Vol. 42, Issue 9 https://doi.org/10.1063/1.1696388	journal	May 1965
Quantitative photoexcitation and fluorescence studies of C ₂ H ₂ in vacuum ultraviolet Suto, Masako; Lee, L. C. The Journal of Chemical Physics, Vol. 80, Issue 10 https://doi.org/10.1063/1.446503	journal	May 1984
Laser-Induced Fluorescence Study of the S ₁ State of Doubly-Substituted ¹³ C Acetylene and Harmonic Force Field Determination Jiang, Jun; Baraban, Joshua H.; Park, G. Barratt The Journal of Physical Chemistry A, Vol. 117, Issue 50 https://doi.org/10.1021/jp407755m	journal	September 2013
Predissociation of acetylene from the Ã 1Au state studied by absorption, laser-induced fluorescence, and H-atom action spectroscopies Suzuki, Toshinori; Hashimoto, Nobuhisa The Journal of Chemical Physics, Vol. 110, Issue 4 https://doi.org/10.1063/1.477868	journal	January 1999
Ultraviolet-Optical Double-Resonance study of the predissociated state of acetylene Lundberg, James K.; Chen, Yongqin; Pique, Jean-Paul Journal of Molecular Spectroscopy, Vol. 156, Issue 1 https://doi.org/10.1016/0022-2852(92)90097-8	journal	November 1992
Communication: An accurate calculation of the S1 C2H2 cis-trans isomerization barrier height Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F. The Journal of Chemical Physics, Vol. 144, Issue 11 https://doi.org/10.1063/1.4943865	journal	March 2016
Notizen: Fluorescence by the Vacuum-uv Photolysis of Acetylene Becker, K. H.; Haaks, D.; Schürgers, M. Zeitschrift für Naturforschung A, Vol. 26, Issue 10 https://doi.org/10.1515/zna-1971-1031	journal	October 1971

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