Isotopic and internal CX3 (X = D,H) rotational motion effects in the Ba⋯FCX3+hν→BaF+CX3 intracluster reactions

Rinaldi, C. A.; Gasmi, K.; Skowronek, S.; González Ureña, A.

doi:doi:10.1063/1.2208618

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Experimental structure determination of silver cluster ions (Agn+,19 ⩽ n ⩽ 79)

The structures of mass selected silver cluster cations Ag19+, Ag38+, Ag55+, Ag59+, Ag75+, and Ag79+ have been probed at a temperature of 100 K by trapped ion electron diffraction. The structure assignment is carried out by comparison of the experimental scattering intensity with theoretical scattering functions of calculated candidate structures obtained by density functional theory. For the cluster sizes studied the resulting experimental data are invariably best described by structures based ...

Identifying reactive trajectories using a moving transition state

A time-dependent no-recrossing dividing surface is shown to lead to a new criterion for identifying reactive trajectories well before they are evolved to infinite time. Numerical dynamics simulations of a dissipative anharmonic two-dimensional system confirm the efficiency of this approach. The results are compared to the standard fixed transition state dividing surface that is well-known to suffer from recrossings and therefore requires trajectories to be evolved over a long time interval befo...

Photodepletion and action spectra of the laser-induced Ba⋯FCD₃ fragmentation have been measured over the 16 075–16 380 cm⁻¹ range. The observed band and peak structures allowed us to estimate the vibrational and rotational structures of the excited complex at the transition state configuration. The relative reaction probability P_R(E) for the intracluster Ba⋯FCD₃+hν→BaF+CD₃ reaction has been determined over the cited energy range. P_R(E) shows a peak structure with an energy spacing of 8.9 cm⁻¹ which was attributed to an internal rotation of the CD₃ group in the intermediate state. A comparison with previous Ba⋯FCH₃ photofragmentation spectra reveals the dynamical role of the internal CX₃ (X = H,D) motion which is manifested by the presence of rotational resonances in the laser-induced intracluster reaction.

Article Outline

INTRODUCTION
EXPERIMENT
RESULTS
DISCUSSION
1. Photodepletion cross section and band structure
2. Structure in the reaction probability energy dependence: Internal CX₃ (X = H,D) rotational effects in the intracluster reaction
CONCLUDING REMARKS

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KEYWORDS and PACS

Keywords

organic compounds, isotope effects, rotational states, photodissociation, photochemistry, reaction kinetics theory, potential energy surfaces, vibrational states

PACS

82.20.Tr

Kinetic isotope effects including muonium
82.20.Db

Transition state theory and statistical theories of rate constants
82.20.Kh

Potential energy surfaces for chemical reactions
82.50.-m

Photochemistry

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http://dx.doi.org/10.1063/1.2208618

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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