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Theoretical Study on the Direction of the Vibrational Transition Dipole Moment of XH Stretching Vibration in HXD
Kaito Takahashi
Institute of Atomic and Molecular Sciences, Academia Sinica, No. 1, Roosevelt Rd., Sec. 4, Taipei 10617, Taiwan
Abstract:
Experimental vibrational spectra of heavy light XH stretching vibrations of simple molecules have been analyzed using the local mode model. In addition, the bond dipole approach, which assumes that the transition dipole moment (TDM) of the XH stretching mode is aligned along the XH bond, has helped analyze experimental spectra. We performed theoretical calculations of the XH stretching vibrations of HOD, HND?, HCD, HSD, HPD?, and HSiD using local mode model and multi-dimensional normal modes. We found that consistent with previous notions, a localized 1D picture to treat the XH stretching vibration is valid even for analyzing the TDM tilt angle. In addition, while the TDM of the OH stretching fundamental transition tilted away from the OH bond in the direction away from the OD bond, that for the XH stretching fundamental of HSD, HND?, HPD?, HCD, and HSiD tilted away from the OH bond but toward the OD bond. This shows that bond dipole approximation may not be a good approximation for the present systems and that the heavy atom X can affect the transition dipole moment direction.
Key words:  heavy light stretching vibration  transition dipole moment  vibrational mode coupling  quantum chemistry  
FundProject:
Theoretical Study on the Direction of the Vibrational Transition Dipole Moment of XH Stretching Vibration in HXD
Kaito Takahashi
Institute of Atomic and Molecular Sciences, Academia Sinica, No. 1, Roosevelt Rd., Sec. 4, Taipei 10617, Taiwan
摘要:
Experimental vibrational spectra of heavy light XH stretching vibrations of simple molecules have been analyzed using the local mode model. In addition, the bond dipole approach, which assumes that the transition dipole moment (TDM) of the XH stretching mode is aligned along the XH bond, has helped analyze experimental spectra. We performed theoretical calculations of the XH stretching vibrations of HOD, HND?, HCD, HSD, HPD?, and HSiD using local mode model and multi-dimensional normal modes. We found that consistent with previous notions, a localized 1D picture to treat the XH stretching vibration is valid even for analyzing the TDM tilt angle. In addition, while the TDM of the OH stretching fundamental transition tilted away from the OH bond in the direction away from the OD bond, that for the XH stretching fundamental of HSD, HND?, HPD?, HCD, and HSiD tilted away from the OH bond but toward the OD bond. This shows that bond dipole approximation may not be a good approximation for the present systems and that the heavy atom X can affect the transition dipole moment direction.
关键词:  heavy light stretching vibration  transition dipole moment  vibrational mode coupling  quantum chemistry  
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