2003
DOI: 10.1021/jp0217785
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Predissociation of Excited Acetylene in the ÃAu State around the Adiabatic Dissociation Threshold as Studied by LIF and H-Atom Action Spectroscopy

Abstract: The LIF and H-atom action spectra of the A ˜-X ˜transition of acetylene in a supersonic jet were observed in the excitation-energy range of 47 000-50 600 cm -1 , where 60 vibrational states were identified in the A state through rotational analyses of respective bands. Most of these states originate from anharmonic couplings of the Franck-Condon-allowed 2 m 3 n states with the 4 i 6 j states where i + j ) even. This fact is consistent with the determined rotational constants of respective states whose values a… Show more

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Cited by 13 publications
(19 citation statements)
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“…These new data have a spectral resolution about 5× better than previous Hatom action spectra of theÃ-X system. 11,36 One particularly important early finding is shown in Figure 1, which shows a hot band going to the K ′ = 2 level of the trans-3 4 6 2 vibrational state. The band is much more prominent in the H-atom action spectrum than in the corresponding LIF spectrum, where overlapping features mostly obscure it.…”
Section: A H-atom Action Spectramentioning
confidence: 91%
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“…These new data have a spectral resolution about 5× better than previous Hatom action spectra of theÃ-X system. 11,36 One particularly important early finding is shown in Figure 1, which shows a hot band going to the K ′ = 2 level of the trans-3 4 6 2 vibrational state. The band is much more prominent in the H-atom action spectrum than in the corresponding LIF spectrum, where overlapping features mostly obscure it.…”
Section: A H-atom Action Spectramentioning
confidence: 91%
“…4 The transition is now known to be a π * ← π excitation from the linear ground state to a trans-bent excited state, S 1 (à 1 A u ). Further detailed analyses by Watson et al, [5][6][7] the Crim group, 8,9 Yamakita and Tsuchiya, [10][11][12] and Merer et al [13][14][15][16][17] have led to an essentially complete assignment of the vibrational and rotational structure up to 4500 cm −1 above the zero-point level of theà state. One of the most interesting results of these analyses has been the discovery 17,18 of bands that belong to the cis-bent isomer of theà state, the zero-point level of which lies about 2670 cm −1 higher in energy than that of the trans-bent isomer.…”
Section: Introductionmentioning
confidence: 99%
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“…The VMP of C 2 H 2 was studied for vibrational preexcitation at energies around that of the 1 CH [10] fundamental, and the 3 CH [8,11,12], 4 CH [2,9] and 5 CH [3][4][5][6][7] overtone stretchings. VMP of C 2 H 2 produces H atoms þ C 2 H radicals, while VMP of C 2 HD offers two distinct isotopic channels, H þ C 2 D and D þ C 2 H. To study these channels C 2 HD was excited, alternatively, to three stretches of CH (3 1 ) [7,5], to two stretches of CH plus one of CC and two CCH bends (2 1 þ 2 þ 2 5 ) [5,7], to four stretches of CH and one of CD (4 1 þ 3 ) [6,7], three stretches of CH plus one of Figure 1.…”
Section: Vmp Of C 2 H 2 and C 2 Hdmentioning
confidence: 99%
“…VMP of the ethyne isotopologues C 2 H 2 [2][3][4][5][6][7][8][9][10][11][12][13] and C 2 HD [6,7,[13][14][15] revealed mode-and bond-selective cleavage of the C-H or C-D bond when the molecules were preexcited to vibrational states in the ground electronic state at energies around that of three, four or five C-H stretches. On the other hand, VMP of three ethyne homologues: (normal) propyne (H 3 CCCH) [16][17][18][19][20], propyne-d 3 (D 3 CCCH) [7,21,22] and 1-butyne (H 3 CH 2 CCCH) [12,19,[23][24][25], pre-excited to energies of up to five C-H acetylenic or alkylic vibrational stretchings, did not show mode-specific cleavage but, nevertheless, in some cases the energy flow out of the pre-excited states indicated mode-dependent coupling with close-lying bath states.…”
Section: Introductionmentioning
confidence: 99%