### Abstract

We apply the adiabatic switching (AS) method to determine the polyatomic classical motions that correspond to selected vibrational quantum states on multidimensional, anharmonic potential energy surfaces, and use these semiclassically quantized motions as initial conditions for quasiclassical trajectory (QCT) calculations of state-to-state reaction dynamics. Specifically, we calculate the classical motion corresponding to the quantum mechanical zero-point vibration of deuterated methane, CD_{4}, and run QCT calculations on the H+CD_{4}→HD(v′, j′)+CD_{3} reaction. The distribution of CD_{4} vibrational zero-point energy (ZPE) associated with the AS-sampled motions is compared with that from normal-mode-sampled motions. The spread of total zero-point energy in the AS calculations is much narrower than with normal-mode sampling, and the ZPE's are appropriately shifted to lower energy due to anharmonic effects. Reverse adiabatic switching is used as an indirect check of the quantum numbers of the adiabatically sampled motion, but numerical limitations made this test inconclusive. The AS method thus appears to be superior to normal-mode sampling, but this superiority cannot be demonstrated conclusively for the fully anharmonic CD_{4} potential. However, the AS method is shown to perform very well for transformation from one CD_{4} harmonic potential to another and for transformation from an harmonic to an anharmonic, but decoupled potential in which CD_{4} is described by Morse oscillators. Evidence is presented that suggests the AS calculations are limited by numerical inaccuracies or intrinsic features of the potential energy surface, both of which are unavoidable. H+CD_{4}→HD(v′ ,j′)+CD _{3} QCT calculations of state-to-state dynamics using CD_{4} with no ZPE, the ZPE from AS sampling, and the ZPE from normal-mode sampling are reported and compared.

Original language | English |
---|---|

Pages (from-to) | 5695-5707 |

Number of pages | 13 |

Journal | Journal of Chemical Physics |

Volume | 102 |

Issue number | 14 |

Publication status | Published - 1995 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*Journal of Chemical Physics*,

*102*(14), 5695-5707.

**Sampling of semiclassically quantized polyatomic molecule vibrations by an adiabatic switching method : Application to quasiclassical trajectory calculations.** / Huang, Jingrong; Valentini, James J.; Muckerman, James.

Research output: Contribution to journal › Article

*Journal of Chemical Physics*, vol. 102, no. 14, pp. 5695-5707.

}

TY - JOUR

T1 - Sampling of semiclassically quantized polyatomic molecule vibrations by an adiabatic switching method

T2 - Application to quasiclassical trajectory calculations

AU - Huang, Jingrong

AU - Valentini, James J.

AU - Muckerman, James

PY - 1995

Y1 - 1995

N2 - We apply the adiabatic switching (AS) method to determine the polyatomic classical motions that correspond to selected vibrational quantum states on multidimensional, anharmonic potential energy surfaces, and use these semiclassically quantized motions as initial conditions for quasiclassical trajectory (QCT) calculations of state-to-state reaction dynamics. Specifically, we calculate the classical motion corresponding to the quantum mechanical zero-point vibration of deuterated methane, CD4, and run QCT calculations on the H+CD4→HD(v′, j′)+CD3 reaction. The distribution of CD4 vibrational zero-point energy (ZPE) associated with the AS-sampled motions is compared with that from normal-mode-sampled motions. The spread of total zero-point energy in the AS calculations is much narrower than with normal-mode sampling, and the ZPE's are appropriately shifted to lower energy due to anharmonic effects. Reverse adiabatic switching is used as an indirect check of the quantum numbers of the adiabatically sampled motion, but numerical limitations made this test inconclusive. The AS method thus appears to be superior to normal-mode sampling, but this superiority cannot be demonstrated conclusively for the fully anharmonic CD4 potential. However, the AS method is shown to perform very well for transformation from one CD4 harmonic potential to another and for transformation from an harmonic to an anharmonic, but decoupled potential in which CD4 is described by Morse oscillators. Evidence is presented that suggests the AS calculations are limited by numerical inaccuracies or intrinsic features of the potential energy surface, both of which are unavoidable. H+CD4→HD(v′ ,j′)+CD 3 QCT calculations of state-to-state dynamics using CD4 with no ZPE, the ZPE from AS sampling, and the ZPE from normal-mode sampling are reported and compared.

AB - We apply the adiabatic switching (AS) method to determine the polyatomic classical motions that correspond to selected vibrational quantum states on multidimensional, anharmonic potential energy surfaces, and use these semiclassically quantized motions as initial conditions for quasiclassical trajectory (QCT) calculations of state-to-state reaction dynamics. Specifically, we calculate the classical motion corresponding to the quantum mechanical zero-point vibration of deuterated methane, CD4, and run QCT calculations on the H+CD4→HD(v′, j′)+CD3 reaction. The distribution of CD4 vibrational zero-point energy (ZPE) associated with the AS-sampled motions is compared with that from normal-mode-sampled motions. The spread of total zero-point energy in the AS calculations is much narrower than with normal-mode sampling, and the ZPE's are appropriately shifted to lower energy due to anharmonic effects. Reverse adiabatic switching is used as an indirect check of the quantum numbers of the adiabatically sampled motion, but numerical limitations made this test inconclusive. The AS method thus appears to be superior to normal-mode sampling, but this superiority cannot be demonstrated conclusively for the fully anharmonic CD4 potential. However, the AS method is shown to perform very well for transformation from one CD4 harmonic potential to another and for transformation from an harmonic to an anharmonic, but decoupled potential in which CD4 is described by Morse oscillators. Evidence is presented that suggests the AS calculations are limited by numerical inaccuracies or intrinsic features of the potential energy surface, both of which are unavoidable. H+CD4→HD(v′ ,j′)+CD 3 QCT calculations of state-to-state dynamics using CD4 with no ZPE, the ZPE from AS sampling, and the ZPE from normal-mode sampling are reported and compared.

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M3 - Article

AN - SCOPUS:0011345314

VL - 102

SP - 5695

EP - 5707

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 14

ER -