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Volumn 125, Issue 8, 2006, Pages

Nonadiabatic effects in the photoelectron spectrum of the pyrazolide-d 3 anion: Three-state interactions in the pyrazolyl-d 3 radical

Author keywords

[No Author keywords available]

Indexed keywords

NONADIABATIC EFFECTS; PHOTOELECTRON ANGULAR DISTRIBUTIONS; QUADRATIC VIBRONIC COUPLING (QVC);

EID: 33748252255     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.2338043     Document Type: Article
Times cited : (68)

References (89)
  • 41
    • 84858930456 scopus 로고    scopus 로고
    • See EPAPS Document No. E-JCPSA6-125-004634 for supplementary tables, figures, and text. This document can be reached via a direct link in the online article's HTML reference section or via the EPAPS homepage (http://www.aip.org/ pubservs/epaps.html).
    • EPAPS Document No. E-JCPSA6-125-004634 , vol.E-JCPSA6-125-004634
  • 49
    • 0003646549 scopus 로고    scopus 로고
    • University of Florida. Integral packages included are the following: J. Almlof and P. R. Taylor, VMOL; P. R. Taylor, VPROPS; and T. Helgaker, H. J. Aa. Jensen, P. Jorgensen, J. Olsen, and P. R. Taylor, ABACUS
    • J. F. Stanton, J. Gauss, J. D. Watts et al., ACES II, a program product of the Quantum Theory Project, University of Florida. Integral packages included are the following: J. Almlof and P. R. Taylor, VMOL; P. R. Taylor, VPROPS; and T. Helgaker, H. J. Aa. Jensen, P. Jorgensen, J. Olsen, and P. R. Taylor, ABACUS.
    • ACES II, A Program Product of the Quantum Theory Project
    • Stanton, J.F.1    Gauss, J.2    Watts, J.D.3
  • 57
    • 33748284168 scopus 로고    scopus 로고
    • note
    • 1 state is ignored in our treatment.
  • 63
    • 33748262143 scopus 로고    scopus 로고
    • note
    • The relative signs of λ parameters reflect those of the corresponding normal coordinates. Only the magnitudes are shown in Table V, while the relative signs are apparent in Table VIII.
  • 69
    • 33748250941 scopus 로고    scopus 로고
    • note
    • Nontotally symmetric modes can show up only in terms of (2v)×n, where n is an integer. The present study does not incorporate anharmonic effects in the adiabatic simulation.
  • 70
    • 33748281812 scopus 로고    scopus 로고
    • note
    • This observation can be used as a check on the convergence of the model Hamiltonian calculation with respect to the number of Lanczos recursion and basis set size.
  • 72
    • 33748267769 scopus 로고    scopus 로고
    • note
    • Certainly, the resonance feature can be reproduced in the adiabatic simulation as long as the anharmonicity of the potential energy surface is taken into account. In the 1-imidazolyl system, the corresponding anharmonicity is associated with one totally symmetric mode (linear) and one vibronic coupling mode (quadratic). Nonadiabatic simulation with quadratic model potentials can accommodate the effects of such anharmonicity as the totally symmetric mode tunes the energy difference of the two vibronically coupled states. See Ref. 2.
  • 73
    • 33748263075 scopus 로고    scopus 로고
    • note
    • The reduction in the number of vibronic coupling modes is made based on the magnitudes of the linear interstate coupling constants. We assume that the diabatic off-diagonal quadratic force constants, which mix these coupling modes, are zero in the treatment of the model potentials. Indeed, we find negligible off-diagonal elements in the force constant matrix evaluated at the anion geometry once contributions from the vibronic interactions are subtracted. Such observation has been made previously for the p-benzoquinone system (Ref. 28). It should be mentioned that the numbers of nuclear basis functions for the totally symmetric modes, on the other hand, cannot be determined simply from the magnitudes of the linear coupling constants because of the mode mixing (see Tables III, IV, and VI).
  • 74
    • 33748266755 scopus 로고    scopus 로고
    • note
    • 1 states. Thus, the effects of this truncation on the final three-state simulation are negligible.
  • 84
    • 33748263659 scopus 로고    scopus 로고
    • note
    • This high sensitivity may imply that a more elaborate treatment of vibronic coupling modes in the model potentials is necessary to provide a more correct representation of the spectral feature of peaks e and f.
  • 85
    • 33748265987 scopus 로고    scopus 로고
    • note
    • 2 state), the quadratic coupling constants are evaluated from the harmonic vibrational frequencies of the anion and neutral states under the parallel mode approximation.


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