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Non-adiabatic dissociation of rovibrationally excited acetylene

Yuval Ganot, Amir Golan, Xinzhi Sheng,y Salman Rosenwaksz and Ilana Barx Department of Physics, Ben-Gurion University of the Negev, Beer-Sheva, 84105, Israel. E-mail: ibar@bgumail.bgu.ac.il Received 29th August 2003, Accepted 21st October 2003 First published as an Advance Article on the web 14th November 2003

The photofragmentation dynamics of acetylene, C2H2 , was explored via vibrationally mediated photodissociation. Direct near infrared (NIR) excitation eciently prepared rovibrational states in the region of three CH stretch quanta ($9640 cm1), subsequently $243.1 nm UV1 photons promoted the pre-excited C2H2 molecules to the A 1Au state and dissociated them and nally the ensuing H atoms were probed by UV2 photons via (2 + 1) resonantly enhanced multiphoton ionization. UV dependent action spectra, monitoring the H photofragment yield vs. the UV1 dissociating laser wavelength displayed sharp peaks depending on the combined energy and the initially excited rovibrational state. These spectra indicate that the rovibrational transitions belonging to the (1112000) combination band, containing trans-bend mode excitation, are excessively enhanced over those of the (0030000) state with three CH stretch quanta, due to favorable FranckCondon (FC) factor. The UV absorption from these states sampled particular rovibronic levels of the potential well on the upper A 1Au state, disclosing transitions to FC active vibronic modes, involving couplings between torsion and cis-bend with C=C stretch and trans-bend modes. These results suggest that the initial state preparation samples the bound rather than the purely repulsive region of the A 1Au state and that the rovibronic structure is the essential factor in aecting the absorption cross-section. They also indicate that the provided energy is insucient to overcome the barrier on the A 1Au state, leading to the dominant non-adiabatic predissociative ~ photofragmentation into C2H (X 2S+) + H.

1. Introduction
Acetylene is an important prototype molecule, bridging the gap between diatomic and large polyatomic molecules and guring in many areas of chemistry. Despite its molecular simplicity, its complex photochemistry and spectroscopy remained quite enigmatic, motivating numerous studies. ~ The ground state of acetylene, X 1S , is of a linear HCCH g equilibrium geometry and isomerizes near 15 000 cm1 to 15 vinylidene, H2CC. The rst excited electronic state, A 1 Au , is of a planar trans-bent geometry.6 As established from ~ absorption and uorescence measurements,68 the A X sys0 tem is dominated by long progressions in n 3 (the excited state 0 0 0 trans-bending mode), n 2 + n 3 (n 2 is the CC stretch mode) and 0 0 0 n 1 + n 3 (n 1 is the CH symmetric stretching). Owing to the strict gerade (g) $ ungerade (u) symmetry selection rules for the centrosymmetric acetylene, it was possible to observe these vibrational states only through transitions from the vibration~ less ground state X 1S . Very recently,9 sixty vibrational states g were observed in the 47 00050 600 cm1 region and most of them were attributed to anharmonic couplings of the Franck 0 0 0 0 Condon (FC) allowed mn 2 + nn 3 states with the in 4 + jn 6 ~ states, where i + j even. The A X transitions to u vibra0 0 tional states, namely n 4 and n 6 , were rst observed by Crim and 10 co-workers in double resonance studies, which reverse the symmetry, and access u instead of g vibrations.912 The spectrum in the 155200 nm region is also rather complex, consist~ ~ ing of diuse bands, and was assigned to the B 1Bu X 1S g
y Permanent address: Department of Physics, Northern Jiaotong University, Beijing 100044 P.R. China z The Helen and Sanford Diller Family Chair in Chemical Physics. x Also at: The Institutes for Applied Research, Ben-Gurion University of the Negev, Beer-Sheva 84105 Israel.

transition, again possessing a long vibrational progression in 0 n 3 and a trans-bent geometry in the upper state.6,7 The common view regarding the mechanism for acetylene photodissociation from both states is that they correlate adiabatically with C2H A2P) + H.13,14 However, the adiabatic connection to C2H (A2P) involves a barrier of 6.48 eV (52 265 cm1),13 conning its ecient production and consequently leading to the competing excited state decay process, namely predissocia~ tion to C2H (X 2S+) + H with a threshold of 5.77 eV (46 538 1 cm ). The non-adiabatic process may occur via two routes: that comprising spin forbidden transitions between the A state and close lying triplet states and that involving transition between singlet states.13,1518 The former is eective already ~ above the threshold energy for C2H (X 2S+) + H production, while the latter requires higher energies. This is because it ~ occurs via A/B crossing at 6.07 eV, followed by a subsequent ~ dissociation barrier on the B state of 6.28 eV.13 ~ The vibrational states in the X 1S ground electronic state g of acetylene have also gained considerable theoretical and experimental attention.1928 This is since it is the simplest molecule representing features relevant to vibrational dynamics in larger polyatomics together with fully resolved spectra up to chemically interesting levels of vibrational excitation.29 In particular, the 3n 3 band, identied as (0030000) in the cluster19,30 or polyad29 model, involving excitation of three quanta of antisymmetric stretch, attracted quite much interest and has been investigated at low and high resolution.19b,21,25,3134 It has been suggested that the (0030000) state, around 9640 cm1, lies closely to other states and therefore couples directly or indirectly with them via anharmonic and a net of Coriolis interactions.19b,25,34 In addition, it has been found that n 1 + n 2 + n 3 + 2n 4 or (1112000), at $9668 cm1, representing a combination band of one quantum of symmetric CH stretch, one of C=C stretch, one of antisymmetric Phys. Chem. Chem. Phys., 2003, 5, 53995404 5399

DOI: 10.1039/b310457e

This journal is # The Owner Societies 2003

CH stretch and two quanta of C=CH trans-bend, lies very close to the (0030000) bright state, directly interacting with it. Other vibrational states were also observed in this energetic region, but are less pronounced.34 Vibrationally mediated photodissociation (VMP),35,36 where upper electronic states are accessed via vibrationally excited states, provides unique means for addressing photophysics and intramolecular dynamics and has been applied to acetylene in several studies. Zhang et al.,37 employed H-Rydberg atom photofragment translational spectroscopy and showed that acetylene excitation to the n 1 + 3n 3 (four CH stretch quanta) vibrational state followed by 248 nm dissociation, i.e., combined (rovibrational + UV) energy of $52 950 cm1, ~ primarily produces C2H (A2P) + H over C2H (X 2S+) + H. This diered markedly from the one-photon 193.3 nm photodissociation, which provided 1200 cm1 less energy and yielded ~ predominantly C2H (X 2S+) + H. We have previously reported on the $243.1 nm photodissociation of initially excited acetylene isotopomers, C2HD and C2H2 in the region of the fourth overtone of the CH stretch38,39 and of the latter also in the region of the third overtone.40 For both species it was suggested that the FC overlap was enhanced for combination bands or for perturbing states containing bend excitation. But even more notable was our observation that the product identity or photodissociation dynamics could be altered by preparation of dierent, adjacent rotational states. This behavior was ascribed to the character of the initially prepared rovi~ brational states in the X 1S ground electronic state, where g some of them were strongly mixed with dark states. In the above VMP studies the dissociation was aected by combined energies higher than the barrier, enabling sampling of the upper potential energy surfaces (PESs) in energetic regions where adiabatic dissociation could occur. In a recent preliminary study41 we showed that pre-excitation in the region of the second overtone of CH stretch of C2HD and C2H2 , followed by $243.1 nm excitation to the upper PES resulted in signicant dierences in their dissociation cross sections. Consequently, the CH(D) bond ssion in C2HD was hindered while in C2H2 considerably enhanced leading to predissociative production of H photofragments. In this article we further examine the eect of the initial rovibrational pre-excitation, in the region of three CH stretch quanta, on the $243 nm dissociation of C2H2 . Fig. 1 presents the idea behind the experiment, generally resembling the previously employed scheme,3640 but using an upgraded system.

Near infrared (NIR) photons energized the C2H2 molecules ~ to a desired rovibrational quantum state of the X 1S ground g electronic state. Then UV1 photons promoted the molecules to the A 1Au bent-state (term value, T0 , of 42 197.57 cm1)8 and nally an additional UV2 laser probed the H photofragments. The total combined energy in these experiments was $50 770 cm1 ($6.29 eV), aording access to the well of the A 1Au state of C2H2 and consequently non-adiabatic dissociation. It is interesting to assess the eect of the CH bond lengthening and of the combined molecular motion on dissociation ecacy and dynamics.

2. Experiment
The experimental apparatus was an upgraded system of that previously used in our studies,39,40 employing in the present experiments three tunable lasers. A pulsed free-jet supersonic beam of C2H2 , diluted to $5% in Ar at a total pressure of $760 Torr, owed through a 0.8 mm orice of a pulsed valve and a skimmer into the ionization region of the time-of-ight mass spectrometer (TOFMS). There it was intersected by the excitation, dissociation and probe laser beams. The background pressure in the chamber prior to experiments was <107 Torr and the typical working pressure $5 106 Torr. The molecular beam at these conditions is characterized by a predominant rotational temperature of 15 K.41 In these experiments the lasers produced light to carry out independently rovibrational excitation, photolysis and resonantly enhanced multiphoton ionization (REMPI) for detection of H photofragments. The NIR light for exciting the second CH stretch overtone region came from the idler output ($10 mJ energy, $0.08 cm1 bandwidth) of an optical parametric oscillator, pumped by the seeded third harmonic of a Nd:yttriumaluminium-garnet (YAG) laser. This beam was focused with a 15 cm focal length (f.l.) lens onto the interaction region of the TOFMS. Following the excitation pulse, after a delay of $10 ns, the photolysis (UV1) laser arrived. This laser was a dye laser pumped by the second harmonic of a Nd:YAG laser. The output of this dye laser was frequency doubled and mixed with the fundamental of the Nd:YAG laser to produce light in the 242.5243.8 nm region. The bandwidth and energy for the UV1 laser were $0.17 cm1 and $250 mJ, respectively. A telescope collimated the photolysis laser beam to a diameter of approximately 5 mm and then the beam was combined by a dichroic beamsplitter with the NIR beam and focused with the above mentioned 15 cm f.l. lens. This resulted in a relatively low power density, minimizing photoproduct ionization. The probe (UV2) beam temporally overlapped the photolysis beam and counterpropagated it. The UV2 beam ($120 mJ energy, $0.4 cm1 bandwidth) originated from a frequency doubled tunable dye laser pumped by the third harmonic of an additional Nd:YAG laser. This beam was focused into the chamber with a 30 cm f.l. lens and employed for detection of the ensuing H photofragments by (2 + 1) REMPI via the two-photon transition, 2s 2S 1s 2S, at 243.135 nm. The temporally overlapping photolysis and probe UV laser beams were delayed with respect to the NIR laser to preclude C2H2 ionization. Ions formed via REMPI in the interaction region of the TOFMS were subjected to continuously biased extraction, two acceleration stages, two pairs of orthogonal deection plates and an Einzel lens prior to entering the eld-free drift region and eventual detection by a microsphere plate. UV dependent action spectra were monitored by setting the NIR laser on particular rovibrational transitions and the UV2 probe laser on the H two-photon transition, while scanning the UV1 photolysis laser. Moreover, H Doppler proles were monitored by xing the NIR and UV1 photolysis lasers on constant wavelengths and tuning the UV2 probe across the H transition.

Fig. 1 Schematics of the rovibrational excitation of C2H2 in the region of three CH stretch quanta by NIR photons followed by their promotion to the excited A 1Au electronic state by UV1 photons, where the molecules decomposed to release H photofragments, detected via (2 + 1) REMPI with UV2 probe photons.

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The ion signals were captured by a boxcar integrator. The data was then directed, via an analog to digital converter, to a personal computer controlling the data acquisition. Each data point in the ensuing spectra is a result of the average of 30150 pulses. Photoacoustic (PA) spectroscopy was used to follow the experimental conditions, to ensure steady rovibrational excitation during measurements of UV action spectra, to calibrate the transition wavenumbers according to data in ref. 33 and to determine the intensity ratios in absorption of the (0030000) and (1112000) bands. The PA signal was monitored using an auxiliary PA cell, lled with $30 Torr of C2H2 and situated at the exit of the TOF chamber.

3. Results
UV action spectra were monitored to assess the eect of the initially prepared vibrational states and the excitation to the A 1Au state on the H atom yield. To aord sampling of identical energetic regions of the A 1Au state (combined energy 1 of 50 61550 820 cm ) the excitation of initially prepared J00 0 of (0030000) and (1112000) was performed by shifted UV1 photons to compensate for the energy dierence in the vibrational excitation. It appears from the UV action spectra, shown in Fig. 2, that sharp transitions are observed for both J00 0 of (0030000) (panel a) and J00 0 of (1112000) (panel b), where those observed in the former are consistent with those in the latter. Nonetheless, the UV action of the latter reveals more transitions, spanning a larger range and implying higher ecacy in excitation to the A 1Au state, although the spectra were not corrected for the $(9.1):(1) ratio of the intermediate state preparation. This ratio was established from the PA spectrum, which showed that the (0030000) state is prepared $9.1 times more eciently than the (1112000) state. The multiple peaks, in the UV action spectrum, could be well tted by Voigt proles with homogeneous rovibronic linewidths of 0.19 (standard deviation s 0.09) cm1, obtained after deconvolution of the 0.17 cm1 laser linewidth. This homogenous linewidth corresponds to a characteristic lifetime of 28 ps. It should be pointed out that all the peaks are exclusively a result of the NIR-UV double resonance, disappearing completely when the NIR beam is blocked. The UV action spectra, obtained as a result of excitation of dierent initially prepared J00 0, 1, and 2 states of (1112000) with combined energies of 50 71550 820 cm1, Fig. 3, show

that numerous features appear and their amount increases with J00 . The spectra of J00 1 and 2 states are lined up to that of J00 0 by shifting these spectra to the blue by 2.32 and 6.97 cm1, respectively. It is revealed that the main features, appearing in the spectrum of J00 0 (panel (a)), form a set of transitions marked by the dashed lines. This set is repeated in the spectra of J00 1 and 2 (panels (b) and (c)) with similar positions. The remaining lines in the spectra of J00 1 and 2 t an additional set of transitions in the former and two additional sets in the latter (see the rulers above the spectra of panels (b) and (c). The shifts of the transition sets of J00 1 and 2 with respect to J00 0 reect the change in J00 during the occurring vibronic transitions. The observed shifts are compatible with Bavg0 of $1.07 cm1, which is similar to that adopted by Crim and co-workers10 for rovibronic levels of ~ the A state. It should be noted that the A ! X band system of acetylene is of the c-type, wherein the rotational selection rules are DJ 0, 1 and DK (K0a l00 ) 1.9 The only possible transitions from (0030000) and (1112000) states ~ (K00 l00 0) in X are those to the J0 ! 1, K0 1 vibronic . Consequently, it is expected that only R(0) lines levels of A should appear for excitation of J00 0, Q(1) and R(1) for J00 1 and P(2), Q(2) and R(2) lines for J00 2. Indeed this is the case, for example the peaks in Fig. 3(a) are R(0) transitions that begin in the (1112000) state and end in J0 1 levels of the A state with dierent vibrational wavefunctions. This double resonance spectrum gives a uniquely clear view of a specic subset of eigenstates in the A state. Furthermore, as seen from the spectra represented in Fig. 3(a)3(c), the number of transition sets increases from one to three, reecting the above selection rules. In addition, H REMPI proles were acquired via double resonance to A 1Au rovibronic states to enable determination of the translational energies of the H photofragments. The proles, as represented by that of J00 4 of C2H2 (1112000) excited with UV photolysing photons of 243.382 nm (Fig. 4) could be well tted by Gaussians. This prole and those obtained in excitation of J00 0 of C2H2 (1112000) and (0030000) to dierent rovibronic states (see below) are characterized, after deconvolution of the laser bandwidth (0.4 cm1)

Fig. 2 UV action spectrum obtained by excitation of the initially prepared J00 0 of (0030000) [panel (a)] and of (1112000) [(panel (b)] to the A 1Au state. The wavenumbers signify the combined energy (NIR + UV1) for excitation of the corresponding rovibrational states to the A 1Au state.

Fig. 3 UV action spectrum obtained by excitation of initially pre pared J00 0, 1, and 2 states of (1112000) to vibronic states of A 1 Au , panels (a)(c), respectively. The wavenumbers for J0 1, and 2 are shifted to t those of J00 0. The vertical dashed line assign the set of transitions corresponding to R(0), Q(1) and P(2) lines excited from the J00 0, 1, and 2 states, respectively. The rulers above the spectra correspond in panel (b) to R(1), and in panel (c) to Q(2) and R(2) transitions. The wavenumbers signify the combined energy (NIR + UV1) for excitation of the corresponding rovibrational states to the A 1Au state.

Phys. Chem. Chem. Phys., 2003, 5, 53995404

5401

modes, comprising dierent molecular motions, inuenced the dissociation. This was, in particular, exemplied in acetylene, where combination bands, comprising bend excitation, were more prominent in the action than in absorption.39,40 Moreover, specic rotational states of C2HD38 mixed with close zero-order dark states of bend character aected considerably the FC factor and bond ssion and most signicantly the H/D branching ratio. For HNCO43 it was shown that the perturbing zero-order state containing bending excitation of the NCO moiety is much more eciently photodissociated than that excited with three quanta of NH stretching zero-order state. Dramatic dierences were also observed for the relative intensities of dierent bands associated with a given CH3Cl isotopomer.44 All these examples show the dependence of the subsequent interaction, i.e., the excitation to the upper electronic state and the dissociation outcome, on the components of the initially prepared eigenstates. (b) The accessed structured region on the A 1Au state

Fig. 4 (2 + 1) REMPI signal of the H atomic photofragment (circles) detected via the 2s 2S ! 1s 2S transition as a function of the UV twophoton wavenumber and the tted Gaussian (solid line). The Doppler prole is obtained following the 243.38 cm1 excitation of the J00 4 of C2H2 (1112000) to the A 1Au state and subsequent predissociation.

by a FWHM of 2.8 (s 0.2) cm1. The estimated maximal translational energy of the H atoms is 0.55 (0.07) eV.

4. Discussion
(a) The 0030000 and 1112000 bands The observed UV action spectra in Fig. 2, which sampled the excitation from J00 0 of (0030000) and (1112000) to rovibro nic states on the upper A 1Au electronic state clearly show that the H atom yield strongly depends on the NIR/UV photon energies. The main reasons for this yield dependence could be, rst, that the NIR photon modies the FC factors for absorption of the UV photon. Second, that the UV photons populate rovibronic levels in the A 1Au state that couple well to dark states (see below) aectively promoting predissociation and hence H atom photofragmentation. This experiment oers the possibility to discern between the two reasons by exciting from the two initially prepared rovibrational states to similar rovibronic states on the upper A 1Au electronic state while using the same combined energy for excitation. Consequently, the access of identical rovibronic states implies similar coupling to close lying dark states and therefore H photofragment yield as a result of alteration of the FC factors. Comparison of panels (a) and (b) of Fig. 2 indicates that the transition probabilities from J00 0 of (1112000) are higher than those from J00 0 of (0030000). The ratio of the integrated intensities of the transitions from the (1112000) state to those from the (0030000) state was found to be 1068, with an average ratio of 27 (s 11). This ratio already accounts for the 9.1:1 intensity ratio of the (0030000):(1112000) bands. Thus, energizing the (1112000) combination band of acetylene, consisting of bending, leads to a higher ecacy in dissociation. This is ascribed to the resemblance of the prepared vibrational wavefunction on the ground state to that on the upper state and accordingly to the improved FC overlap between them. Therefore, the enhanced FC factor for the intermediate state ~ containing C=CH bending increases the A 1AuX 1S absorpg tion and promotes the CH bond cleavage more eciently. This signicantly larger enhancement is consistent with previous ndings,36,3840,4345 where excitation of dierent 5402 Phys. Chem. Chem. Phys., 2003, 5, 53995404

The UV dependent action spectra of Figs. 2 and 3 show that a very structured spectral region on the bound portion of the upper A 1Au state is accessed. It is recognized that due to the strict selection rules in acetylene only u states are FC allowed and might be accessed in our experiment. Therefore, 0 0 these states might consist of in 6 (n 6 768.3 cm1) (bu) (anti0 0 symmetric cis-in plane bend) and jn 4 (n 4 764.9 cm1) (au) (torsion) vibrational modes, where i + j odd. These states are expected to closely resonate via Coriolis interactions10 0 and probably DarlingDennison coupling (trade two n 4 for 0 two n 6 quanta). Very recently Yamakita et al.9 measured sixty transitions in the 47 00050 600 cm1 region by one photon excitation from the vibrationless ground state and then transitions up to 53 500 cm1 by IR-UV double resonance from a single rotational level of the antisymmetric CH stretching n 300 state. They attributed the accessed states to interactions 0 0 0 0 of n 2 and n 3 progressions with n 4 /n 6 states, which result in a 29,46 polyad structure. Particularly, in the former region the 0 0 0 0 n 2 and n 3 of symmetry are bright states and the n 4 /n 6 of u symmetry are dark states (i.e., having no FC factor with the ~ vibrationless ground state of the X state), while in the latter 0 vice versa, whereas an even or odd quantum number of n 4 / 0 n 6 contributes, respectively. It is likely that at the high vibra tional energy within the A state accessed in our experiment, the vibrational levels become also signicantly anharmonically 0 0 coupled. This is in addition to the previously mentioned n 4 /n 6 couplings and occurs via the cubic anharmonic coupling (trade 0 0 0 0 one quantum of n 2 or n 3 for two of n 4 or n 6 modes). Therefore, it seems that the encountered lines come from these polyads, where the appearance of so many lines results from the preexcitation of the (1112000) state, which contains bending and consequently an improved FC factor. (c) Dissociation dynamics from the 0030000 and 1112000 states

The initial vibrational pre-excitation extends the CH bond in the 0030000 state or excites the CH, C=C bonds and the C=CH trans-bend mode in the 1112000 state on the ground state potential of C2H2 . Nevertheless, the subsequent electronic transition, in both cases, is still to the bound portion of the A 1Au state and not to its repulsive region, allowing access of sharp resonances. Some insight into these resonances can be revealed by considering the possible candidates for coupling. In the accessed energetic region of $57 070 cm1, the A state (singlet S1) might interact with rovibrational levels of the close ~ lying T3 and T2,1 triplet states, and with those of the X (S0) 13 ground state. Given that the manifold of T3 levels is less dense than those of T2,1 and S0 and also since earlier ndings pointed out that the coupling of S1 to dark states is facilitated by S1T3 interactions,13,47,48 it is presumed that T3 is the key

player. The intersystem crossing to the doorway T3 states is probably aided by the initial excitation of torsion and bending. Since the dissociation of the acetylene molecule on T3 is unikely,13 the molecule presumably crosses to the dark T1,2 states and nally to S0 , where it dissociates via the C2H ~ (X 2S+) + H non-adiabatic pathway. These mechanisms provide a rationale for the observed Gaussian tted Doppler prole of Fig. 4. This prole and those obtained in the dissociation of dierent rovibrational states of C2H2 that the departing H atoms were released with maximal translational energy of 0.55 0.07 eV. This translational energy is close to the dierence between the overall photon energy acquired by the molecule via the IR + UV excitation (6.29 eV) and the energy required for photodissociation through the ~ non-adiabatic channel C2H (X 2S+) + H (5.71 eV), which is 0.58 eV.13 This energy similarity indicates that the dissociation of vibrationally excited C2H2 occurs non-adiabatically. Our results can be compared to those of Zhang et al.37 in another double resonance (IR + UV) experiment, where acetylene was excited to the (n 1 + 3n 3) vibrational level (four quanta of CH stretch) and then dissociated by $ 248 nm photons. In that case the dominant product channel was C2H (A 2P) + H, diering markedly from the one-photon 193.3 nm photodissociation, which provided 1200 cm1 less energy and yielded pri~ marily C2H (X 2S+) + H. It should be noted that in the $248 nm photodissociation of (n 1 + 3n 3),37 the combined energy ($52 950 cm1) just exceeds the calculated barrier on the A 1 13 Au state, while in the 193.3 nm dissociation it is just below it, leading to adiabatic and non-adiabatic processes, respec tively. The observation of C2H (A 2P) was attributed to either the excess energy overcoming a barrier or to the moving of the FC region due to vibrational excitation.37 Our results indicate that the former factor dictates whether the occurrence of the photofragmentation will be via adiabatic or non-adiabatic pathway.

the James Franck Binational GermanIsraeli Program in LaserMatter Interaction is also gratefully acknowledged.

References
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5. Conclusions
The $243.1 nm dissociation of C2H2 from selected rovibrational states in the region of the second CH stretch overtone provides new insights on the photofragmentation dynamics. The initial vibrational preparation alters the FC factor for the subsequent transition to the upper A 1Au state, resulting in preferential enhancement of the CH bond cleavage for excitation from the (1112000) state over that from (0030000). However, the main factor in driving the dissociation is the subsequent excitation to the bound portion of the A 1Au state, were numerous vibronic states are accessed. These states originate from couplings between the FC allowed 0 0 in 4 + jn 6 (i + j odd) modes involving torsion and antisym0 0 metric cis-in plane bend with the n 2 and n 3 states. The availability of the vibronic states leads to the existence of sharp structures in the absorption cross-section of C2H2 , aecting extensively the action spectra. The initially prepared noneigenstates on S1 interact with T3 states, which then cross to T1,2 and nally to S0 , where they dissociate, primarily yielding ~ C2H (X 2S+) + H products. This behavior shows that the initial state preparation in this region does not aord sampling of the purely repulsive portion of the A 1Au state and that the non-adiabatic exit channel is dominant due to the involved barrier on the C2H (A2 P) adiabatic channel.

Acknowledgements
We appreciate the critical reading of the manuscript by Professor P. J. Dagdigian. The support of this research by the Israeli Science Foundation (ISF) under grant No. 29/99-2 and by

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n 3 represent s and s CH stretches and n 4 and n 5 the pg and pu g u trans- and cis-bend, respectively, while n 2 is the CC stretch (s ). g The superscripts, l4 and l5 denote vibrational angular momentum quantum numbers (ref. 31). G. Herzberg, Molecular spectra and molecular structure. II. Infrared and Raman spectra of polyatomic molecules, Van Nostrand Reinhold, New York, 1945. S. Ghersetti, J. E. Adams and N. K. Rao, J. Mol. Spectrosc., 1977, 64, 157. L. N. Sinitsa, J. Mol. Spectrosc., 1980, 84, 57. M. Herman, T. R. Huet and M. Vervloet, Mol. Phys., 1989, 66, 333. F. F. Crim, J. Phys. Chem., 1996, 100, 12 725. I. Bar and S. Rosenwaks, Int. Rev. Phys. Chem., 2001, 20, 711. J. Zhang, C. W. Riehn, M. Dulligan and C. Wittig, J. Chem. Phys., 1995, 103, 6815. T. Arusi-Parpar, R. P. Schmid, R.-J. Li, I. Bar and S. Rosenwaks, Chem. Phys. Lett., 1997, 268, 163; R. P. Schmid, Y. Ganot, S. Rosenwaks and I. Bar, J. Mol. Struct., 1999, 480481, 197. R. P. Schmid, T. Arusi-Parpar, R.-J. Li, I. Bar and S. Rosenwaks, J. Chem. Phys., 1997, 107, 385; R. P. Schmid, Y. Ganot, I. Bar and S. Rosenwaks, J. Chem. Phys., 1998, 109, 8959;

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T. Arusi-Parpar, R. P. Schmid, Y. Ganot, I. Bar and S. Rosenwaks, Chem. Phys. Lett., 1998, 287, 347. X. Sheng, Y. Ganot, S. Rosenwaks and I. Bar, J. Chem. Phys., 2002, 117, 6511. Y. Ganot, X. Sheng, I. Bar and S. Rosenwaks, Chem. Phys. Lett., 2002, 361, 175. Y. Ganot, S. Rosenwaks and I. Bar, unpublished. E. Woods III, H. L. Berghout, C. M. Cheatum and F. F. Crim, J. Phys. Chem. A, 2000, 104, 10 356. C. Tao and P. J. Dagdigian, Chem. Phys. Lett., 2001, 350, 63. H. Akagi, K. Yokoyama and A. Yokoyama, J. Chem. Phys., 2003, 118, 3600. 0 If the anharmonic coupling occurs between a single quantum of n 3 0 0 0 and two quanta of n 4 or n 6 than the nn 3 splits into (n + 1)(n + 2)/2 0 0 0 0 states.9 For example the 3n 3 yields ten states: 3n 3 , 2n 3 + 2n 4 , 0 0 0 0 0 0 0 0 0 0 0 0 2n 3 + 2n 6 , n 3 + 4n 4 , n 3 + 2n 4 + 2n 6 , n 3 + 4n 6 , 6n 4 , 4n 4 + 2n 6 and 0 0 0 2n 4 + 4n 6 , 6n 6 . M. Drabbels, J. Heinz and W. L. Meerts, J. Chem. Phys., 1994, 100, 165. P. Dupre, Chem. Phys., 1995, 196, 239; P. Dupre, P. G. Green and R. W. Field, Chem. Phys., 1995, 196, 211.

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