Time-dependent dynamics of methyl iodide photodissociation in the first continuum

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Abstract

The photodissociation dynamics of methyl iodide (CH3I) and its deuterated counterpart (CD3I) in the A band is studied using a time-dependent quantum mechanical method, based on the fast Fourier transform (FFT) method of Kosloff and Kosloff. The calculation uses a pseudotriatomic approximation in which the umbrella mode of CH3 (CD3) is approximated by a C-X (X = H3, D3) stretch. In addition, the I-C-X dissociation is assumed collinear and angular momentum is ignored. The wave packet is propagated on coupled electronic potential surfaces which we have developed by revising Shapiro's potentials to fit recent experimental data. Good agreement between our calculations and experiment has been obtained for the absorption spectrum, the vibrational distributions for the methyl umbrella mode, and I*/I branching ratios for both CH3I and CD 3I at 248 nm. According to our model, the CH3 fragment in the I* channel at 266 nm is predominantly at its ground vibrational state, while the vibrational distribution in the lower I channel extends to ν = 6 and has a peak at ν = 1.

Original languageEnglish
Pages (from-to)393-402
Number of pages10
JournalJournal of Chemical Physics
Volume93
Issue number1
Publication statusPublished - 1990

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Photodissociation
photodissociation
iodides
continuums
Wave packets
Angular momentum
vibrational states
Fast Fourier transforms
wave packets
Absorption spectra
angular momentum
fragments
dissociation
absorption spectra
momentum
approximation
electronics
Experiments
methyl iodide

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Time-dependent dynamics of methyl iodide photodissociation in the first continuum. / Guo, Hua; Schatz, George C.

In: Journal of Chemical Physics, Vol. 93, No. 1, 1990, p. 393-402.

Research output: Contribution to journalArticle

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abstract = "The photodissociation dynamics of methyl iodide (CH3I) and its deuterated counterpart (CD3I) in the A band is studied using a time-dependent quantum mechanical method, based on the fast Fourier transform (FFT) method of Kosloff and Kosloff. The calculation uses a pseudotriatomic approximation in which the umbrella mode of CH3 (CD3) is approximated by a C-X (X = H3, D3) stretch. In addition, the I-C-X dissociation is assumed collinear and angular momentum is ignored. The wave packet is propagated on coupled electronic potential surfaces which we have developed by revising Shapiro's potentials to fit recent experimental data. Good agreement between our calculations and experiment has been obtained for the absorption spectrum, the vibrational distributions for the methyl umbrella mode, and I*/I branching ratios for both CH3I and CD 3I at 248 nm. According to our model, the CH3 fragment in the I* channel at 266 nm is predominantly at its ground vibrational state, while the vibrational distribution in the lower I channel extends to ν = 6 and has a peak at ν = 1.",
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N2 - The photodissociation dynamics of methyl iodide (CH3I) and its deuterated counterpart (CD3I) in the A band is studied using a time-dependent quantum mechanical method, based on the fast Fourier transform (FFT) method of Kosloff and Kosloff. The calculation uses a pseudotriatomic approximation in which the umbrella mode of CH3 (CD3) is approximated by a C-X (X = H3, D3) stretch. In addition, the I-C-X dissociation is assumed collinear and angular momentum is ignored. The wave packet is propagated on coupled electronic potential surfaces which we have developed by revising Shapiro's potentials to fit recent experimental data. Good agreement between our calculations and experiment has been obtained for the absorption spectrum, the vibrational distributions for the methyl umbrella mode, and I*/I branching ratios for both CH3I and CD 3I at 248 nm. According to our model, the CH3 fragment in the I* channel at 266 nm is predominantly at its ground vibrational state, while the vibrational distribution in the lower I channel extends to ν = 6 and has a peak at ν = 1.

AB - The photodissociation dynamics of methyl iodide (CH3I) and its deuterated counterpart (CD3I) in the A band is studied using a time-dependent quantum mechanical method, based on the fast Fourier transform (FFT) method of Kosloff and Kosloff. The calculation uses a pseudotriatomic approximation in which the umbrella mode of CH3 (CD3) is approximated by a C-X (X = H3, D3) stretch. In addition, the I-C-X dissociation is assumed collinear and angular momentum is ignored. The wave packet is propagated on coupled electronic potential surfaces which we have developed by revising Shapiro's potentials to fit recent experimental data. Good agreement between our calculations and experiment has been obtained for the absorption spectrum, the vibrational distributions for the methyl umbrella mode, and I*/I branching ratios for both CH3I and CD 3I at 248 nm. According to our model, the CH3 fragment in the I* channel at 266 nm is predominantly at its ground vibrational state, while the vibrational distribution in the lower I channel extends to ν = 6 and has a peak at ν = 1.

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