Photofragmentation of HI in the first continuum

Veen, G. N. A. van; Mohamed, K.A.; Baller, T.; Vries, A.E. De

doi:10.1016/0301-0104(83)85172-6

Cited by 76 publications

(34 citation statements)

References 16 publications

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“…Finally we note that the angular distributions reveal all three states in the photofragmentation of HI [47]. Considering the range of photofragment results now available a further investigation of the MCD spectra would be very valuable.…”

Section: State Symmetriesmentioning

confidence: 85%

Photofragmentation dynamics of n-C₃H₇I and i-C₃H₇I at 248 nm

1987

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Translational photofragment spectroscopy has been used to study the photodissociation dynamics of n-C3HTI and i-C3HTI at 248 nm. The measured anisotropies of the photofragments show that the initial absorption is the (parallel polarized) 3Qo*--N transition with a dissociation lifetimes of 3.7 + 2 x 10 13s and 2.5 + 2 x 10-13s respectively. The time of flight measurements yield the energy disposal for channels leading to I(2P3/2) and I*(2P1/2) for both molecules, although with greater uncertainty for i-C3H7I. The average energy disposed into translation is 43 per cent (I) and 52 per cent (I*) for n-C3H7I , and 39 per cent (I) and 57 per cent (I*) for i-C3H7I.The energy disposal for a variety of alkyl iodides are found to be well described by an impulsive model of the dissociation dynamics with the niodoalkanes showing a near constant width for the translational energy distribution regardless of its absolute value. A simple Landau-Zener curve crossing description is used to highlight the substantial change in curve crossing probability caused by substitution at the fl carbon or change to a secondary structure for the radical. Finally a model which combines the soft-radical impulse model for energy disposal with the Landau-Zener curve crossing probability is found to provide an excellent description of the I* quantum yields for the n-iodoalkanes.

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Section: State Symmetriesmentioning

confidence: 85%

Photofragmentation dynamics of n-C₃H₇I and i-C₃H₇I at 248 nm

1987

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“…The question arises as to the mechanism of the curve crossing, which could be due to either vibrational or rotational coupling. The strength of the coupling arising from Coriolis interaction is expected to be very small [26], especially in the supersonically cooled molecular beam and, indeed, no curve crossing is observed between the corresponding states in HI [27] where only this interaction is possible. Vibronic coupling requires an e mode vibration to be excited in the E(1Q) state to provide the necessary overall A 1 symmetry to allow radial coupling to the Ml(3Q0) state.…”

Section: IImentioning

confidence: 99%

Photofragmentation dynamics of CH₃I at 248 nm

1984

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The vibrational distributions of the methyl fragment resulting from the photodissociation of CHzI at 248 nm are obtained by TOF photofragment spectroscopy. Only excitation of the v 2 (umbrella) mode is observed and the distribution peaks strongly at v = 2 for the electronically adiabatic pathway (I zP1/2) but extends up to v = 8 for the minor (~ 30 per cent) non-adiabatic pathway (12P3/~). Angular measurements show that both pathways result from an initial parallel ('~Q0 +-N) transition followed by a curve crossing to produce the ground state I fragment. The coupling of the curves is vibronic in nature and probably involves the v~ methyl rocking mode. The lifetime of the photodissociation is found to be ~ 1 x 10 -13 s.

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“…Thus, the Doppler line profile provides information on the H atom recoil energy, the a:gular distribution (whether H atom is produced in parallel or perpendicular transition) and the branching ratio for I( 2 PI/ 2 ) and I( 2 P 3 / 2 ). Photofragment TOF measurements of the H atom produced in the photolysis of HI at 248, 222, and 193 nm have also been recently reported (184). Two peaks were observed in the TOF spectra, and each of these peaks had a different polarization dependence.…”

Section: Hi( T H + I( Pa2mentioning

confidence: 79%

“…TOF measurements at 266 nm had already shown that both fragments are produced. Van Veen et al (184) and Barry and Gorry (188) show that this is also the case at 248 nm. Van Veen et al also measured the anisotropy parameter, showing that it is appropriate for the 3Q 0 <-1A 1 transition, so that ground state iodine atoms must be produced as a result of a curve crossing between the 3 Q 0 state and the IQ state.…”

Section: B Methyl Iodidementioning

confidence: 81%

Photodissociation Dynamics of Small Molecules

Jackson¹,

Okabe²

1986

Advances in Photochemistry

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Photofragmentation of HI in the first continuum

Cited by 76 publications

References 16 publications

Photofragmentation dynamics of n-C₃H₇I and i-C₃H₇I at 248 nm

Photofragmentation dynamics of n-C₃H₇I and i-C₃H₇I at 248 nm

Photofragmentation dynamics of CH₃I at 248 nm

Photodissociation Dynamics of Small Molecules

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Photofragmentation of HI in the first continuum

Cited by 76 publications

References 16 publications

Photofragmentation dynamics of n-C3H7I and i-C3H7I at 248 nm

Photofragmentation dynamics of n-C3H7I and i-C3H7I at 248 nm

Photofragmentation dynamics of CH3I at 248 nm

Photodissociation Dynamics of Small Molecules

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Photofragmentation dynamics of n-C₃H₇I and i-C₃H₇I at 248 nm

Photofragmentation dynamics of n-C₃H₇I and i-C₃H₇I at 248 nm

Photofragmentation dynamics of CH₃I at 248 nm