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Volumn 109, Issue 11, 1998, Pages 4396-4406

The rotational spectrum of a highly vibrationally mixed quantum state. I. Intramolecular vibrational energy redistribution (IVR) exchange narrowing of the rotational spectrum

Author keywords

[No Author keywords available]

Indexed keywords

CONVERGENCE OF NUMERICAL METHODS; EIGENVALUES AND EIGENFUNCTIONS; MATHEMATICAL MODELS; MATRIX ALGEBRA; SPECTROSCOPY; STATISTICAL METHODS;

EID: 0032529985     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.477043     Document Type: Article
Times cited : (21)

References (43)
  • 24
    • 0004020426 scopus 로고
    • The rotational dependence of the transition dipole moment would be more important for comparing spectra at different J values and can be easily added to this formulation Dover, New York
    • The rotational dependence of the transition dipole moment would be more important for comparing spectra at different J values and can be easily added to this formulation: C. H. Townes and A. L. Schawlow, Microwave Spectroscopy (Dover, New York, 1975).
    • (1975) Microwave Spectroscopy
    • Townes, C.H.1    Schawlow, A.L.2
  • 28
    • 22244490924 scopus 로고    scopus 로고
    • bright〉
    • bright〉.
  • 29
    • 22244465162 scopus 로고
    • This form of the line shape has also been discussed for the vibrational spectrum of a highly vibrationally excited molecule
    • This form of the line shape has also been discussed for the vibrational spectrum of a highly vibrationally excited molecule: A. A. Stuchebrukhov and I. E. Khromov, Chem. Phys. Lett. 134, 251 (1987).
    • (1987) Chem. Phys. Lett. , vol.134 , pp. 251
    • Stuchebrukhov, A.A.1    Khromov, I.E.2
  • 30
    • 22244446728 scopus 로고    scopus 로고
    • One additional manipulation of the Hamiltonian is required to satisfy the motional narrowing commutation relations. To ensure that the zeroth-order and motional terms commute, the zeroth-order Hamiltonian should be made proportional to the identity matrix. This can be achieved by taking the average energy in the region of interest as the energy for all of the zeroth-order states. The differences in energy for each state from this reference energy can then be placed in the diagonal matrix elements of the perturbation term
    • One additional manipulation of the Hamiltonian is required to satisfy the motional narrowing commutation relations. To ensure that the zeroth-order and motional terms commute, the zeroth-order Hamiltonian should be made proportional to the identity matrix. This can be achieved by taking the average energy in the region of interest as the energy for all of the zeroth-order states. The differences in energy for each state from this reference energy can then be placed in the diagonal matrix elements of the perturbation term.
  • 32
    • 0010890275 scopus 로고
    • This description of the rotational spectroscopy is the basis of Fourier Transform Microwave Spectroscopy
    • This description of the rotational spectroscopy is the basis of Fourier Transform Microwave Spectroscopy: J. C. McGurk, T. G. Schmalz, and W. H. Flygare, Adv. Chem. Phys. 25, 1 (1974).
    • (1974) Adv. Chem. Phys. , vol.25 , pp. 1
    • McGurk, J.C.1    Schmalz, T.G.2    Flygare, W.H.3
  • 33
    • 0001077721 scopus 로고
    • There is one additional technical point in choosing the mean level spacing for the line shape normalization. The actual state density used is one-third the state density used for the calculation. This factor of 3 reduction is required to account for the intensity fluctuations expected for ergodic spectra and is often called Heller's F
    • There is one additional technical point in choosing the mean level spacing for the line shape normalization. The actual state density used is one-third the state density used for the calculation. This factor of 3 reduction is required to account for the intensity fluctuations expected for ergodic spectra and is often called Heller's F: E. J. Heller, J. Chem. Phys. 92, 1718 (1990).
    • (1990) J. Chem. Phys. , vol.92 , pp. 1718
    • Heller, E.J.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.