The spectroscopy, photophysics and photodissociation dynamics of jet-cooled CF<sub>3</sub>NO[Ã(n,π*)]

Dyet, Julie A.; McCoustra, Martin R. S.; Pfab, Josef

doi:10.1039/f29888400463

Cited by 27 publications

(39 citation statements)

References 3 publications

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“…22,32 As in the photodissociation of CNP, dissociation of CF 3 NO produces two fragments with disparate rotational constants. As a result PST will predict substantially different v-j correlations for the CF 3 and NO fragments.…”

Section: Cf 3 Nomentioning

confidence: 99%

Classical phase space theory for product state distributions with application to the v–j vector correlation

Klippenstein

Cline

1995

The Journal of Chemical Physics

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A classical phase space theory procedure for estimating product state distributions for ''barrierless'' dissociations is described. The distributions are determined in terms of an average over the available phase space on a fixed dividing surface of the function describing the distribution of interest. The use of a weighting function corresponding to the contribution of each randomly sampled phase space point to the number of available states, as in related state counting algorithms, provides an efficient route to the determination of any particular product state distribution or correlation. The coordinates employed in this sampling are the Euler angles, describing the orientation in space of each of the fragments and of the line of centers connecting the two fragments, and their conjugate momenta. Sample applications focus on the determination of the vector correlation between the angular momentum of one fragment and the relative velocity of the fragments for the dissociations of 2-chloro-2-nitrosopropane ͑CNP͒, NCCN, and CF 3 NO. Comparisons with the corresponding experimental measurements for the CNP and NCCN dissociations provide further evidence for the presence of important dynamical effects in these dissociations. The calculations for CF 3 NO are presented with the hope of motivating an experimental verification of the predicted strong v-j correlation for the CF 3 fragment in combination with the weak correlation for the NO fragment. Overall, these phase space theory results are found to provide a useful reference for the interpretation of experimental results.

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Section: Cf 3 Nomentioning

confidence: 99%

Classical phase space theory for product state distributions with application to the v–j vector correlation

Klippenstein

Cline

1995

The Journal of Chemical Physics

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“…For some nitroso compounds the rotational distributions become slightly nonstatistical at the shortest wavelengths in this absorption. 7,13 The nonstatistical spinorbit population ratio, observed over a wide wavelength range for several compounds, 3,4,7,13,17 was tentatively attributed to the participation of the T 1 dissociation channel. 14 More recently, measurements of photoproduct recoil speed distributions and -v-j angular correlations of the NO fragment have been measured for the 2-chloro-2nitrosopropane, 1-chloro-1-nitrosocyclohexane, and 2-chloro-2-nitroso-6,6-dimethylbicycloheptane at the shorter end of the 600-700 nm photolysis wavelength range.…”

Section: Introductionmentioning

confidence: 94%

“…Experimental studies of the 450-700 nm photodissociation dynamics of NCNO, 1-3 ͑CH 3 ͒ 3 CNO, 4,5 HNO, 6 CF 3 NO, 7-13 CF 2 ClNO, 14 CFCl 2 NO, 15 and C͑CH 3 ͒ 2 ClNO [16][17][18] have been reported and a general picture of the gas phase photofragmentation mechanism of nitrosoalkanes has emerged. In this wavelength range the absorption is assigned to a S 1 Ã 1 AЉ←S 0 X 1 AЈ͓n(N),*(NϭO)͔ transition.…”

Section: Introductionmentioning

confidence: 99%

Scalar and angular correlations in CF3NO photodissociation: statistical and nonstatistical channels

Spasov

Cline

1999

The Journal of Chemical Physics

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Evidence for the onset of three-body decay in photodissociation of vibrationally excited CHFCl 2Picosecond real time study of the bimolecular reaction O ( 3 P)+ C 2 H 4 and the unimolecular photodissociation of CH 3 CHO and H 2 CO Polarized 1ϩ1Ј REMPI combined with TOFMS detection was used to obtain recoil speed distributions, NO product rotational distributions, andv-j NO angular correlations in the photofragmentation of CF 3 NO between 585 and 650 nm. At wavelengths longer than 610 nm dissociation occurs only on the S 0 potential energy surface of CF 3 NO. At 585 nm the product recoil speed distribution is bimodal, with the higher speed component attributed to dissociation across a potential barrier on the T 1 surface. Measurements of the T 1 channel NO product trajectory show it has no laboratory frame rotational alignment or recoil anisotropy, but has a significant preference for vЌj NO angular correlation, reaching a maximal value of ␤ 0 0 (22)ϭϪ0.308Ϯ0.052. The results are interpreted using the results of statistical phase space theory and classical trajectory calculations. It is concluded that S 0 channel dissociation occurs by a statistical dissociation mechanism whereas the T 1 channel dynamics is dominated by exit channel recoil forces due to a potential barrier.

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“…We used the results of the studies [1][2][3][4][5][6][7][8][9][10] for comparison with the results of ab initio calculations. Before proceeding to numerical experiments (Section 3), let us describe the concepts forming the background for the use of one-dimensional potential curves for internal rotation.…”

Section: Introductionmentioning

confidence: 99%

“…These molecules are sufficiently small for high-level ab initio calculations and they are characterized by a simple form of the internal rotation potential. In addition, the structures of the molecules under consideration were experimentally studied by microwave [1,2], vibrational [3,4], and vibronic [5][6][7][8][9][10] spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

One-dimensional models of internal rotation in CX3NO molecules (X=H, D, F)

Dolgov

Bataev

Пупышев

et al. 2005

Journal of Molecular Spectroscopy

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The spectroscopy, photophysics and photodissociation dynamics of jet-cooled CF₃NO[Ã(n,π*)]

Cited by 27 publications

References 3 publications

Classical phase space theory for product state distributions with application to the v–j vector correlation

Classical phase space theory for product state distributions with application to the v–j vector correlation

Scalar and angular correlations in CF3NO photodissociation: statistical and nonstatistical channels

One-dimensional models of internal rotation in CX3NO molecules (X=H, D, F)

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The spectroscopy, photophysics and photodissociation dynamics of jet-cooled CF3NO[Ã(n,π*)]

Cited by 27 publications

References 3 publications

Classical phase space theory for product state distributions with application to the v–j vector correlation

Classical phase space theory for product state distributions with application to the v–j vector correlation

Scalar and angular correlations in CF3NO photodissociation: statistical and nonstatistical channels

One-dimensional models of internal rotation in CX3NO molecules (X=H, D, F)

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The spectroscopy, photophysics and photodissociation dynamics of jet-cooled CF₃NO[Ã(n,π*)]