Full nine-dimensional ab initio potential energy surfaces and trajectory studies of A-band photodissociation dynamics

CH3I*→CH3+I, CH3+I*, and CD3I*→CD3+I, CD3+I*

Yoshiaki Amatatsu, Satoshi Yabushita, Keiji Morokuma

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Abstract

The full nine-dimensional potential energy surfaces (PESs) of the 3Q0 and 1Q1 states of CH3I have been calculated with the ab initio contracted spin-orbit configuration interaction method. The results are fitted to three diabatic potential terms and their couplings as functions of all the internal degrees of freedom. The transition dipole at the Franck-Condon region has also been calculated. Surface hopping quasiclassical trajectory calculations on these potential energy surfaces have been performed to examine the photodissociation dynamics of both CH3I and CD3I in the A-continuum. The results are in general good agreement with the recent experimental findings. The reasonable I*/(I*+I) branching ratio can be obtained with these PESs when the contribution of direct transition to the 1Q1 state is considered. The rotational distribution of the CH3 and CD3 fragments and its I*/(I*+I)-channel selectivity are determined by the shape of the PESs with respect to the bending angle outside the conical intersection region. The vibrational distribution of umbrella mode is closely related to the shape of PESs for the umbrella angle; the sudden switch of reaction coordinate from 3Q0 to 1Q1 at the conical intersection is the origin of vibrational excitation in the I* channel. The larger umbrella excitation of the CD3 fragment in both I and I* channels, in comparison with the CH3 fragment, is related to the larger separation of the reaction coordinate from the Franck-Condon geometry. The symmetric stretching energy increases during the dissociation, which is related to the shape of PESs with respect to this coordinate, and the excitation of symmetric stretching mode seems to be possible.

Original languageEnglish
Pages (from-to)9783-9794
Number of pages12
JournalJournal of Chemical Physics
Volume104
Issue number24
Publication statusPublished - 1996 Jun 22

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Photodissociation
Potential energy surfaces
photodissociation
potential energy
Trajectories
trajectories
fragments
Stretching
intersections
excitation
Orbits
configuration interaction
Switches
switches
degrees of freedom
selectivity
dissociation
dipoles
Geometry
continuums

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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title = "Full nine-dimensional ab initio potential energy surfaces and trajectory studies of A-band photodissociation dynamics: CH3I*→CH3+I, CH3+I*, and CD3I*→CD3+I, CD3+I*",
abstract = "The full nine-dimensional potential energy surfaces (PESs) of the 3Q0 and 1Q1 states of CH3I have been calculated with the ab initio contracted spin-orbit configuration interaction method. The results are fitted to three diabatic potential terms and their couplings as functions of all the internal degrees of freedom. The transition dipole at the Franck-Condon region has also been calculated. Surface hopping quasiclassical trajectory calculations on these potential energy surfaces have been performed to examine the photodissociation dynamics of both CH3I and CD3I in the A-continuum. The results are in general good agreement with the recent experimental findings. The reasonable I*/(I*+I) branching ratio can be obtained with these PESs when the contribution of direct transition to the 1Q1 state is considered. The rotational distribution of the CH3 and CD3 fragments and its I*/(I*+I)-channel selectivity are determined by the shape of the PESs with respect to the bending angle outside the conical intersection region. The vibrational distribution of umbrella mode is closely related to the shape of PESs for the umbrella angle; the sudden switch of reaction coordinate from 3Q0 to 1Q1 at the conical intersection is the origin of vibrational excitation in the I* channel. The larger umbrella excitation of the CD3 fragment in both I and I* channels, in comparison with the CH3 fragment, is related to the larger separation of the reaction coordinate from the Franck-Condon geometry. The symmetric stretching energy increases during the dissociation, which is related to the shape of PESs with respect to this coordinate, and the excitation of symmetric stretching mode seems to be possible.",
author = "Yoshiaki Amatatsu and Satoshi Yabushita and Keiji Morokuma",
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T1 - Full nine-dimensional ab initio potential energy surfaces and trajectory studies of A-band photodissociation dynamics

T2 - CH3I*→CH3+I, CH3+I*, and CD3I*→CD3+I, CD3+I*

AU - Amatatsu, Yoshiaki

AU - Yabushita, Satoshi

AU - Morokuma, Keiji

PY - 1996/6/22

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N2 - The full nine-dimensional potential energy surfaces (PESs) of the 3Q0 and 1Q1 states of CH3I have been calculated with the ab initio contracted spin-orbit configuration interaction method. The results are fitted to three diabatic potential terms and their couplings as functions of all the internal degrees of freedom. The transition dipole at the Franck-Condon region has also been calculated. Surface hopping quasiclassical trajectory calculations on these potential energy surfaces have been performed to examine the photodissociation dynamics of both CH3I and CD3I in the A-continuum. The results are in general good agreement with the recent experimental findings. The reasonable I*/(I*+I) branching ratio can be obtained with these PESs when the contribution of direct transition to the 1Q1 state is considered. The rotational distribution of the CH3 and CD3 fragments and its I*/(I*+I)-channel selectivity are determined by the shape of the PESs with respect to the bending angle outside the conical intersection region. The vibrational distribution of umbrella mode is closely related to the shape of PESs for the umbrella angle; the sudden switch of reaction coordinate from 3Q0 to 1Q1 at the conical intersection is the origin of vibrational excitation in the I* channel. The larger umbrella excitation of the CD3 fragment in both I and I* channels, in comparison with the CH3 fragment, is related to the larger separation of the reaction coordinate from the Franck-Condon geometry. The symmetric stretching energy increases during the dissociation, which is related to the shape of PESs with respect to this coordinate, and the excitation of symmetric stretching mode seems to be possible.

AB - The full nine-dimensional potential energy surfaces (PESs) of the 3Q0 and 1Q1 states of CH3I have been calculated with the ab initio contracted spin-orbit configuration interaction method. The results are fitted to three diabatic potential terms and their couplings as functions of all the internal degrees of freedom. The transition dipole at the Franck-Condon region has also been calculated. Surface hopping quasiclassical trajectory calculations on these potential energy surfaces have been performed to examine the photodissociation dynamics of both CH3I and CD3I in the A-continuum. The results are in general good agreement with the recent experimental findings. The reasonable I*/(I*+I) branching ratio can be obtained with these PESs when the contribution of direct transition to the 1Q1 state is considered. The rotational distribution of the CH3 and CD3 fragments and its I*/(I*+I)-channel selectivity are determined by the shape of the PESs with respect to the bending angle outside the conical intersection region. The vibrational distribution of umbrella mode is closely related to the shape of PESs for the umbrella angle; the sudden switch of reaction coordinate from 3Q0 to 1Q1 at the conical intersection is the origin of vibrational excitation in the I* channel. The larger umbrella excitation of the CD3 fragment in both I and I* channels, in comparison with the CH3 fragment, is related to the larger separation of the reaction coordinate from the Franck-Condon geometry. The symmetric stretching energy increases during the dissociation, which is related to the shape of PESs with respect to this coordinate, and the excitation of symmetric stretching mode seems to be possible.

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