Collisional energy transfer probabilities of highly excited molecules from KCSI. III. Azulene: P(E ',E) and moments of energy transfer for energies up to 40 000 cm(-1) via self-calibrating experiments

2003 | journal article. A publication with affiliation to the University of Göttingen.

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​Collisional energy transfer probabilities of highly excited molecules from KCSI. III. Azulene: P(E ',E) and moments of energy transfer for energies up to 40 000 cm(-1) via self-calibrating experiments​
Hold, U.; Lenzer, T.; Luther, K. & Symonds, A. C.​ (2003) 
The Journal of Chemical Physics119(21) pp. 11192​-11211​.​ DOI: https://doi.org/10.1063/1.1622382 

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Authors
Hold, U.; Lenzer, T.; Luther, Klaus; Symonds, A. C.
Abstract
Complete experimental transition probability density functions P(E-',E) have been determined for collisions between highly vibrationally excited azulene and several bath gases over a wide energy range. This was achieved by applying 2-color "kinetically controlled selective ionization (KCSI)" [U. Hold, T. Lenzer, K. Luther, K. Reihs, and A. C. Symonds, J. Chem. Phys. 112, 4076 (2000)]. The results are "self-calibrating," i.e., independent of any empirical calibration curve, as usually needed in traditional energy transfer experiments like time-resolved ultraviolet absorption or infrared fluorescence. The complete data set can be described by our recently introduced monoexponential 3-parameter P(E-',E) form with a parametric exponent Y in the argument, P(E-',E)proportional toexp[-{(E-E-')/(C-0+C-1.E)}(Y)]. For small colliders (helium, argon, xenon, N-2, and CO2) the P(E-',E) show increased amplitudes in the wings compared to a monoexponential form (Y<1). For larger colliders, the wings of P(E-',E) have an even smaller amplitude (Y>1) than that provided by a monoexponential. Approximate simulations show that the wings of P(E-',E) at amplitudes <1x10(-6) (cm(-1))(-1) have a nearly negligible influence on the population distributions and the net energy transfer. All optimized P(E-',E) representations exhibit a linear energy dependence of the collision parameter alpha(1)(E)=C-0+C-1.E, which also results in an (approximately) linear dependence of <DeltaE> and <DeltaE(2)>(1/2). The energy transfer parameters presented in this study have benchmark character in certainty and accuracy, e.g., with only 2%-5% uncertainty for our <DeltaE> data below 25 000 cm(-1). Deviations of previously reported first moment data from ultraviolet absorption and infrared fluorescence measurements can be traced back to either the influence of azulene self-collisions or well-known uncertainties in calibration curves. (C) 2003 American Institute of Physics.
Issue Date
2003
Status
published
Publisher
Amer Inst Physics
Journal
The Journal of Chemical Physics 
ISSN
0021-9606

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