FULL-DIMENSIONALITY QUANTUM CALCULATIONS OF ACETYLENE/VINYLIDENE ISOMERIZATION
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Date
2003
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Publisher
Ohio State University
Abstract
The isomerization of acetylene to vinylidene is examined theoretically in full-dimensionality (six degrees-of-freedom) using a new ab initio potential energy $surface^{a}$. Eigenfunctions and eigenvalues of the exact Hamiltonian, for zero total angular momentum, are obtained using a series of novel truncation/recoupling procedures that permits calculations up to very high energies. The Hamiltonian is given in diatom-diatom Jacobi coordinates, with the choice $H_{2}-C_{2}$ for the two diatoms to exploit the full permutational symmetry of the problem. By examining expectation values of the eigenfunctions, a number of states are clearly identified with vinylidene-like characteristics. Corresponding calculations are also done for $C_{2}D_{2}$. Full dimensional simulations of the photodetachment spectra of $[C_{2}H_{2}]^{-}$ and $[C_{2}D_{2}]^{-}$ are done (within the Franck-Condon approximation) and compared to the experimental ones.
Description
$^{a}$S. Zou and J. M. Bowman, Chem. Phys. Lett. 368, 421 (2003).
Author Institution: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University
Author Institution: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University