Intramolecular dynamics. I. Curvilinear normal modes, local modes, molecular anharmonic Hamiltonian, and application to benzene | Zendy

Yongfeng Zhang | Zendy; Stephen J. Klippenstein | Zendy; R. A. Marcus | Zendy

Open Access

Intramolecular dynamics. I. Curvilinear normal modes, local modes, molecular anharmonic Hamiltonian, and application to benzene

Author(s) -

Yongfeng Zhang,

Stephen J. Klippenstein,

R. A. Marcus

Publication year - 1991

Publication title -

the journal of chemical physics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.071

H-Index - 357

eISSN - 1089-7690

pISSN - 0021-9606

DOI - 10.1063/1.460216

Subject(s) - anharmonicity , curvilinear coordinates , quartic function , normal coordinates , hamiltonian (control theory) , normal mode , intramolecular force , potential energy , physics , kinetic energy , hamiltonian matrix , chemistry , classical mechanics , quantum mechanics , mathematics , vibration , molecule , eigenvalues and eigenvectors , symmetric matrix , mathematical optimization , pure mathematics

The Hamiltonian based on curvilinear normal modes and local modes (CNLM) is discussed using Wilson's exact vibrational Hamiltonian as basis, the CNLM representation diagonalizing only the normal mode block of FG matrix in curvilinear internal coordinates. Using CNLM the kinetic and potential energy operators for benzene are given, including cubic and quartic anharmonicity in the potential energy and cubic and quartic terms in the kinetic energy expansion in curvilinear coordinates. Using symmetrized coordinates and cubic and higher force constants the number and identity of the independent symmetry allowed (A1g) such force constants are obtained. The relation to conventional anharmonic force constants is then given and the allowed contributions of the latter are obtained. The results are applied to CH overtone spectra and intramolecular vibrational dynamics in Part III of this series.

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