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Stert, V.; Farmanara, P.; Radloff, W.; Noack, F.; Skowronek, S.; Jiménez, Josué; Ureña, A. González

doi:10.1103/physreva.59.r1727

Cited by 26 publications

(18 citation statements)

References 22 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: 65%

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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: 65%

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

et al. 2005

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“…The first one implies a significant alteration of the calcium electronic structure that brings a level of calcium within the excitation region. This can be due either to a substantial electron transfer between Ca and CH 3 F in the excited state, or to the promotion of the excited electron to a Rydberg orbital, stabilized by the interaction with CH 3 F. The second tentative explanation was invoked due to the observation of structures in the action spectrum, an observation that makes the present Ca/CH 3 F system very different from the apparently similar Ba/CH 3 F system (Ca and Ba are both alkaline earth atoms) studied in the groups of Ureña [17,18,19,20,21,22] and Radloff [23,24,25,26,27]. The structures observed in the Ca/CH 3 F system were tentatively assigned to the C-F stretch in the CH 3 F molecule, suggesting that this stretch plays an important role in the dynamics of turning on the reaction.…”

Section: Introductionmentioning

confidence: 89%

“…The Na/HF [9], Li, Na/HF, CH 3 F [10,11,5], Na 2 /CH 3 Cl [12], Ca/HX [13,14,15,16] and Ba/CH 3 F [17,18,19,20,21,22] systems were explored using the latter technique. Realtime studies have also been performed on the Ba/CH 3 F system [23,24,25,26,27].…”

Section: Introductionmentioning

confidence: 99%

Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 2. Experimental and Ab Initio Studies of the Free Ca···FCH₃ Complex

et al. 2006

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The Ca* + CH 3 F f CaF* + CH 3 reaction was photoinduced in 1:1 Ca‚‚‚CH 3 F complexes formed in a supersonic expansion. The transition state of the reaction was explored by monitoring the electronically excited product, CaF, while scanning the laser that turns on the reaction. Moreover, the electronic structure of the Ca‚‚‚FCH 3 system was studied using ab initio methods by associating a pseudopotential description of the [Ca 2+ ] and [F 7+ ] cores, a core polarization operator on calcium, an extensive Gaussian basis and a treatment of the electronic problem at the CCSD(T) (ground state) and RSPT2 (excited states) level. In this contribution we present experimental results for the free complex and a comparison with the results of a previous experiment where the Ca‚‚‚CH 3 F complexes are deposited at the surface of large argon clusters. The ab initio calculations allowed an interpretation of the experimental data in terms of two reaction mechanisms, one involving a partial charge transfer state, the other involving the excitation of the C-F stretch in the CH 3 F moiety prior to charge transfer.

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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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Real-time study of the femtosecond harpooning reaction inBa⋯FCH3

Cited by 26 publications

References 22 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

Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 2. Experimental and Ab Initio Studies of the Free Ca···FCH₃ Complex

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

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Real-time study of the femtosecond harpooning reaction inBa⋯FCH3

Cited by 26 publications

References 22 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

Transition State Spectroscopy of the Photoinduced Ca + CH3F Reaction. 2. Experimental and Ab Initio Studies of the Free Ca···FCH3 Complex

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

Transition State Spectroscopy of the Photoinduced Ca + CH₃F Reaction. 2. Experimental and Ab Initio Studies of the Free Ca···FCH₃ Complex