Ultrafast dynamics and energetics of the intracluster harpooning reaction in Ba⋯FCH3

Farmanara, P.; Stert, V.; Radloff, W.; Skowronek, S.; Ureña, A. Gonzalez

doi:10.1016/s0009-2614(99)00318-8

Cited by 24 publications

(16 citation statements)

References 9 publications

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“…Something new happens in the latter system that does not seem relevant of the local excitation that prevails in the Ca · · · HBr experiment. This is very unexpected not only because of the present comparison with the Ca · · · HBr system but also because local excitation of the metal moiety prevails in all the apparently similar complexes that were investigated so far: complexes between an alkali atom and halogen containing molecules [12,[42][43][44][45][46][47][48][49] or a complex between barium and CH 3 F [15,19,23,25]. Local excitation has also been found in many excited metal ion complexes such as Mg + CH 3 I described in Ref.…”

Section: Discussionsupporting

confidence: 59%

“…Situations that are apparently similar, have been examined in free complex experiments by Polanyi and coworkers on 1:1 Li · · · CH 3 F [12] and by Ureña, Radloff and coworkers on Ba · · · FCH 3 [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. We shall see the that dynamics of the present Ca · · · CH 3 F system is significantly different from the latter dynamics.…”

Section: Introductionmentioning

confidence: 66%

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Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 1. A Cluster Isolated Chemical Reaction Study

et al. 2005

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The "Cluster Isolated Chemical Reactions" technique is used to examine the dynamics of the photoinduced reaction producing electronically excited CaF when 1:1 Ca · CH 3 F complexes are deposited at the surface of large argon clusters. This technique ensures quantitatively that 1:1 complexes are actually at the origin of the observed signals. The reaction is monitored by observing the CaF chemiluminescence while scanning the photoexcitation laser. The resulting action spectrum contains information about the absorption bands of the complex, filtered by the dynamics of the reaction. The observations suggest a profound alteration of the calcium electronic structure and a control of the reaction by the CF stretch in CH 3 F.

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Section: Discussionsupporting

confidence: 59%

Section: Introductionmentioning

confidence: 66%

Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 1. A Cluster Isolated Chemical Reaction Study

et al. 2005

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“…12,15 In Fig. 9 the time-dependent ion signals for the BaF reaction product are displayed as obtained in the earlier experiments without infrared preexcitation.…”

Section: Resultsmentioning

confidence: 92%

Control of breaking strong versus weak bonds of BaFCH3 by femtosecond IR + VIS laser pulses: theory and experiment

Lippert

Manz

Oppel

et al. 2004

Phys. Chem. Chem. Phys.

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Intense (E80 GW cm À2 ) ultrashort (E100 fs) infrared (IR) laser pulses may be employed for excitation of a high frequency (E3500 cm À1 ) local mode vibration in a molecule. Subsequently, an intense (16-256 GW cm À2 ), ultrashort visible (VIS) laser pulse yields electronic excitation with near adiabatic transfer of the vibrational energy, which has been accumulated by the IR pulse. The net result of these sequential IR þ VIS laser pulses may be the breaking of a strong molecular bond close to the pre-excited one. In contrast, exclusive excitation by just a visible laser pulse breaks a competing weak bond. The effects of IR þ VIS laser pulse control may be considered as an extension of vibrationally mediated chemistry, from ns pulses or continuous wave (cw) excitations to sub-ps laser pulses, and from direct vibrational pre-excitation of the bond to be broken to a neighboring bond, thus exploiting intramolecular vibrational redistribution (IVR) from the pre-excited local mode to the bond to be broken in the electronic excited state. The mechanism is demonstrated by quantum simulations for the model system BaFCH 3 , where BaF-, FC-and CH 3 play the roles of the weak and strong bonds to be broken, and the vibrationally pre-excited CH 3 stretch. The theoretical predictions are confirmed experimentally. Various extensions of the control by IR þ VIS laser pulses include the control of the branching ratio of weak versus strong bond breaking, as well as isotopomer selectivity depending on the vibrational pre-excitations.

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“…After the first experiments by Soep and co-workers on Ca-HX systems, 18 -22 there have been several other studies on related systems by the groups of Polanyi, [23][24][25][26][27] González-Ureña, 28 -30 etc. More recently also time resolved experiments 31,32 have opened the possibility of following the evolution of the reaction in real time and also to ''control'' the course of the reaction by properly designed excitation pulses. These kind of results provide detailed information about the excited electronic states and about the nonadiabatic couplings governing the transitions between the different electronic states correlating to different final states of products.…”

Section: Introductionmentioning

confidence: 99%

Transition state spectroscopy of the excited electronic states of LiHF

Sanz-Sanz

Roncero

Paniagua

et al. 2002

Chemical Physics Letters

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In this work the LiHF(A,B,BЈ←X) electronic spectrum is simulated and compared with the experimental one obtained by Hudson et al. ͓J. Chem. Phys. 113, 9897 ͑2000͔͒. High level ab initio calculations of three 2 AЈ and one 2 AЉ electronic states have been performed using a new atomic basis set and for a large number of nuclear configurations ͑about 6000͒. Four analytic global potential energy surfaces have been fitted. The spectrum involved very excited rovibrational states, close to the first dissociation limit, at high total angular momentum. Two different methods have been used, one based on bound state and the second one on wave packet calculations. Different alternatives have been used to simulate the relatively high temperatures involved. The agreement obtained with the experimental spectrum is very good allowing a very simple assignment of the peaks. They are due to bending progressions on the three excited electronic states. A simple model is used in which only rotational degrees of freedom are included, which simulates the spectrum in excellent agreement with the experimental one, providing a nice physical interpretation. Moreover, the remaining theoretical/experimental discrepancies have been attributed to nonadiabatic effects through the extension of this model to a diabatic representation of excited coupled electronic states.

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Ultrafast dynamics and energetics of the intracluster harpooning reaction in Ba⋯FCH3

Cited by 24 publications

References 9 publications

Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 1. A Cluster Isolated Chemical Reaction Study

Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 1. A Cluster Isolated Chemical Reaction Study

Control of breaking strong versus weak bonds of BaFCH3 by femtosecond IR + VIS laser pulses: theory and experiment

Transition state spectroscopy of the excited electronic states of LiHF

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Ultrafast dynamics and energetics of the intracluster harpooning reaction in Ba⋯FCH3

Cited by 24 publications

References 9 publications

Transition State Spectroscopy of the Photoinduced Ca + CH3F Reaction. 1. A Cluster Isolated Chemical Reaction Study

Transition State Spectroscopy of the Photoinduced Ca + CH3F Reaction. 1. A Cluster Isolated Chemical Reaction Study

Control of breaking strong versus weak bonds of BaFCH3 by femtosecond IR + VIS laser pulses: theory and experiment

Transition state spectroscopy of the excited electronic states of LiHF

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Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 1. A Cluster Isolated Chemical Reaction Study

Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 1. A Cluster Isolated Chemical Reaction Study