### Abstract

This paper describes several efficient basis optimization methods that we have developed in the application of S-matrix Kohn variational method to quantum reactive scattering. Specifically, we employ a minimum-K body-fixed representation combined with the use of quasiadiabatic basis functions for the expansion of the full reactive scattering wave function. This new basis function approach significantly reduces the size of the "larger" matrix of the final linear algebraic equation in the calculation of reaction cross sections. The accuracy of the calculation can be easily controlled by systematically increasing or decreasing the values of two parameters K_{max} and α, and convergence to the full basis set results can be reached. Numerical test calculations are carried out for the 3D H + H_{2} reaction for the total angular momentum J = 10 and for the 3D F + H_{2} reaction for J = 0, 1, and 2. These calculations demonstrate that our basis optimization approach is very efficient for computing reaction cross sections. Since variational scattering calculations are ultimately limited by the size of the basis set, our method is a stride forward in the applications of variational approach to quantum reactive scattering.

Original language | English (US) |
---|---|

Pages (from-to) | 6047-6054 |

Number of pages | 8 |

Journal | The Journal of chemical physics |

Volume | 94 |

Issue number | 9 |

State | Published - 1991 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

**Progress of basis optimization techniques in variational calculation of quantum reactive scattering.** / Zhang, John.

Research output: Contribution to journal › Article

*The Journal of chemical physics*, vol. 94, no. 9, pp. 6047-6054.

}

TY - JOUR

T1 - Progress of basis optimization techniques in variational calculation of quantum reactive scattering

AU - Zhang, John

PY - 1991

Y1 - 1991

N2 - This paper describes several efficient basis optimization methods that we have developed in the application of S-matrix Kohn variational method to quantum reactive scattering. Specifically, we employ a minimum-K body-fixed representation combined with the use of quasiadiabatic basis functions for the expansion of the full reactive scattering wave function. This new basis function approach significantly reduces the size of the "larger" matrix of the final linear algebraic equation in the calculation of reaction cross sections. The accuracy of the calculation can be easily controlled by systematically increasing or decreasing the values of two parameters Kmax and α, and convergence to the full basis set results can be reached. Numerical test calculations are carried out for the 3D H + H2 reaction for the total angular momentum J = 10 and for the 3D F + H2 reaction for J = 0, 1, and 2. These calculations demonstrate that our basis optimization approach is very efficient for computing reaction cross sections. Since variational scattering calculations are ultimately limited by the size of the basis set, our method is a stride forward in the applications of variational approach to quantum reactive scattering.

AB - This paper describes several efficient basis optimization methods that we have developed in the application of S-matrix Kohn variational method to quantum reactive scattering. Specifically, we employ a minimum-K body-fixed representation combined with the use of quasiadiabatic basis functions for the expansion of the full reactive scattering wave function. This new basis function approach significantly reduces the size of the "larger" matrix of the final linear algebraic equation in the calculation of reaction cross sections. The accuracy of the calculation can be easily controlled by systematically increasing or decreasing the values of two parameters Kmax and α, and convergence to the full basis set results can be reached. Numerical test calculations are carried out for the 3D H + H2 reaction for the total angular momentum J = 10 and for the 3D F + H2 reaction for J = 0, 1, and 2. These calculations demonstrate that our basis optimization approach is very efficient for computing reaction cross sections. Since variational scattering calculations are ultimately limited by the size of the basis set, our method is a stride forward in the applications of variational approach to quantum reactive scattering.

UR - http://www.scopus.com/inward/record.url?scp=0000094490&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000094490&partnerID=8YFLogxK

M3 - Article

VL - 94

SP - 6047

EP - 6054

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 9

ER -