Photoinduced charge-transfer dissociation in van der Waals complexes. V. Na⋯XCH3 (X=F, Cl, and Br)

Chang, Xiao; Ehlich, R.; Hudson, Andrew J.; Polanyi, J. C.; Wang, Jie-Lei

doi:10.1063/1.473511

Cited by 25 publications

(25 citation statements)

References 35 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: 60%

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: 60%

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

et al. 2005

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“…The complexes were identifled by photoionization time-of-flight mass spectrometry. This obtained by ab hitio calculation [96], for the appropriate electronic transition in the complex. This will indicate the probability with which depletion occurs on each excited-state PES.…”

Section: Discussionmentioning

confidence: 99%

“…In addition. the assignment of the photodepletion peaks previously proposed for the system Na-FCH3 has been revised based on more accurate ab initio calculations [96].…”

Section: Discussionmentioning

confidence: 99%

“…The measured photodepletion peaks were found to contain reproducible structure which was believed to arise from vibrational levels of the complex. A b [nitio calculation of the structures of the ground and electronically-excited states, along with the frequencies for the vibrational modes [96] will be used to assist assignment of the observed…”

Section: Discussionmentioning

confidence: 99%

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Dynamics of harpooning studied by transition state spectroscopy. Part III. Li···FCH3

Hudson

Naumkin

et al. 2001

Faraday Disc.

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This manuscri pt has been reproduced from the microfilm master. UMI fi!ms the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer.The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction.In the unlikely event that the author did not send UMI a complete manuscri pt and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion.Oversize materials (e.g., maps, drawings, charts) are reproduced by sectiaoning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps.Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. BeH CanadaThe author has granted a nonexclusive licence allowing the National Library of Canada to reproduce, loan, distribute or sell copies of this thesis in microform, paper or electronic formats.The author retains ownership of the copyright in this thesis. Neither the thesis nor substantial extracts fkom it may be printed or othewise reproduced without the author's permission. Your t m Vorre mlsrsnceOur fi& Notre relereme L'auteur a accorde une licence non exclusive pennettant a la Bibliotheque nationale du Canada de reproduire, prster, distribuer ou vendre des copies de cette these sous la forme de rnicrofiche/film, de reproduction sur papier ou sur format electronique.L'auteur conserve la propriete du droit d'auteur qui protege cette these. Ni la these ni des extraits substantiels de celle-ci ne doivent 6tre imprimes ou autrement reproduits sans son autorisation. The van der Waals complexes. Na-XR (X=F. C1. Br, R=CH3; and X=F. R=H), have been generated by crossing a beam of sodium with the expansion region of a supersonic jet of the appropriate halide in an inert-carrier gas. The complexes were identifled by photoionization time-of-flight mass spectrometry.Depletion of the complexes was observed following photoexcitation using a broad range of wavelengths. 711. Initial excitation of the N a chromophore within the complex is believed to be followed by charge-transfer dissociation;An experimental study of the photodepletion of Na-XR complexes has been made, and the results have been compared to recent ab initio studies of the same process. Photoexcitation of Na-XR accesses a potential-energy surface (PES) for the reaction Na*+XR+NaX+R, at a configuration intermediate between the reactants. Na*+XR, and products. NaX+R. We. therefore. den0 te the excited-state species as a transition state. TS, indica...

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“…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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Photoinduced charge-transfer dissociation in van der Waals complexes. V. Na⋯XCH3 (X=F, Cl, and Br)

Cited by 25 publications

References 35 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

Dynamics of harpooning studied by transition state spectroscopy. Part III. Li···FCH3

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

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Photoinduced charge-transfer dissociation in van der Waals complexes. V. Na⋯XCH3 (X=F, Cl, and Br)

Cited by 25 publications

References 35 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

Dynamics of harpooning studied by transition state spectroscopy. Part III. Li···FCH3

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

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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