High-lying rovibrational states of floppy X3 triatomics by a new D3h symmetry adapted method

Application to the H3 + molecule

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Abstract

A new D3h, symmetry adapted approach to accurate calculation of high-lying rovibrational (J>0) states of floppy X3 triatomic molecules is presented, extending our recent work on J = O bound states of D3h triatomics [Z. Bačić and J. Z. H. Zhang, Chem. Phys. Lett. 184, 513 (1991)]. Three sets of Jacobi coordinates are employed, allowing construction of basis sets with full S3 permutation symmetry of the three identical nuclei. Inclusion of S3 symmetry reduces substantially the size of the final matrix eigenvalue problem and the computational effort involved. It also assures unambiguous, correct symmetry assignment of the calculated rovibrational levels. Our method is especially suitable for rotating D3h molecules with strongly coupled large amplitude motions of the three atoms. An efficient quasiadiabatic diagonalization and truncation scheme is incorporated into our methodology. Application to H3 + for J=1 produced the total of 426 well converged, symmetry assigned states up to ∼24 000 cm-1 above the ground state, far more than in any previous calculation for rotating H 3 +.

Original languageEnglish (US)
Pages (from-to)3707-3713
Number of pages7
JournalThe Journal of chemical physics
Volume96
Issue number5
StatePublished - 1992

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Molecules
symmetry
Ground state
molecules
Atoms
triatomic molecules
permutations
eigenvalues
inclusions
methodology
nuclei
ground state
approximation
atoms

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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title = "High-lying rovibrational states of floppy X3 triatomics by a new D3h symmetry adapted method: Application to the H3 + molecule",
abstract = "A new D3h, symmetry adapted approach to accurate calculation of high-lying rovibrational (J>0) states of floppy X3 triatomic molecules is presented, extending our recent work on J = O bound states of D3h triatomics [Z. Bačić and J. Z. H. Zhang, Chem. Phys. Lett. 184, 513 (1991)]. Three sets of Jacobi coordinates are employed, allowing construction of basis sets with full S3 permutation symmetry of the three identical nuclei. Inclusion of S3 symmetry reduces substantially the size of the final matrix eigenvalue problem and the computational effort involved. It also assures unambiguous, correct symmetry assignment of the calculated rovibrational levels. Our method is especially suitable for rotating D3h molecules with strongly coupled large amplitude motions of the three atoms. An efficient quasiadiabatic diagonalization and truncation scheme is incorporated into our methodology. Application to H3 + for J=1 produced the total of 426 well converged, symmetry assigned states up to ∼24 000 cm-1 above the ground state, far more than in any previous calculation for rotating H 3 +.",
author = "Zlatko Bacic and John Zhang",
year = "1992",
language = "English (US)",
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T1 - High-lying rovibrational states of floppy X3 triatomics by a new D3h symmetry adapted method

T2 - Application to the H3 + molecule

AU - Bacic, Zlatko

AU - Zhang, John

PY - 1992

Y1 - 1992

N2 - A new D3h, symmetry adapted approach to accurate calculation of high-lying rovibrational (J>0) states of floppy X3 triatomic molecules is presented, extending our recent work on J = O bound states of D3h triatomics [Z. Bačić and J. Z. H. Zhang, Chem. Phys. Lett. 184, 513 (1991)]. Three sets of Jacobi coordinates are employed, allowing construction of basis sets with full S3 permutation symmetry of the three identical nuclei. Inclusion of S3 symmetry reduces substantially the size of the final matrix eigenvalue problem and the computational effort involved. It also assures unambiguous, correct symmetry assignment of the calculated rovibrational levels. Our method is especially suitable for rotating D3h molecules with strongly coupled large amplitude motions of the three atoms. An efficient quasiadiabatic diagonalization and truncation scheme is incorporated into our methodology. Application to H3 + for J=1 produced the total of 426 well converged, symmetry assigned states up to ∼24 000 cm-1 above the ground state, far more than in any previous calculation for rotating H 3 +.

AB - A new D3h, symmetry adapted approach to accurate calculation of high-lying rovibrational (J>0) states of floppy X3 triatomic molecules is presented, extending our recent work on J = O bound states of D3h triatomics [Z. Bačić and J. Z. H. Zhang, Chem. Phys. Lett. 184, 513 (1991)]. Three sets of Jacobi coordinates are employed, allowing construction of basis sets with full S3 permutation symmetry of the three identical nuclei. Inclusion of S3 symmetry reduces substantially the size of the final matrix eigenvalue problem and the computational effort involved. It also assures unambiguous, correct symmetry assignment of the calculated rovibrational levels. Our method is especially suitable for rotating D3h molecules with strongly coupled large amplitude motions of the three atoms. An efficient quasiadiabatic diagonalization and truncation scheme is incorporated into our methodology. Application to H3 + for J=1 produced the total of 426 well converged, symmetry assigned states up to ∼24 000 cm-1 above the ground state, far more than in any previous calculation for rotating H 3 +.

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