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Volumn 105, Issue 18, 1996, Pages 8136-8141

On the zero point energy in classical trajectory computations

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Indexed keywords


EID: 0013606318     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.472668     Document Type: Article
Times cited : (61)

References (51)
  • 21
    • 85033042052 scopus 로고    scopus 로고
    • note
    • Specifically, for a Hamiltonian with self anharmonicity terms one cannot use a harmonic approximation. We emphasized this in our original paper (Ref. 10) and reiterate this point below. Guo et al. (Ref. 15) have not followed our procedure and so the results they report do not constitute a test of our method.
  • 26
    • 0001293858 scopus 로고
    • And this is used in the computations of spectra for harmonic potentials. See, for example D. Tannor and E. J. Heller, J. Chem. Phys. 77, 202 (1982).
    • (1982) J. Chem. Phys. , vol.77 , pp. 202
    • Tannor, D.1    Heller, E.J.2
  • 29
    • 85033059764 scopus 로고    scopus 로고
    • note
    • Within our approximation that f(x) is sufficiently slowly varying that its derivative is constant, Eq. (11), this pair of variables is, in fact, canonical {f(x),p} = 1. where the curly brackets are the Poisson brackets. Of course, this is not exactly consistent with Eq. (13). The factorization method (Ref. 27) has identified all the potentials for which the factorization (7)-(9) is exact.
  • 30
    • 85033069083 scopus 로고    scopus 로고
    • note
    • Nor is it reasonable to use x for f(x) as was apparently done in Ref. 15. As noted therein, the harmonic approximation can introduce spurious resonances which are not evident in the exact dynamics and this is the reason for the unphysical oscillations reported there. The (self) anharmonicities need to be realistically handled.
  • 31
    • 85033061490 scopus 로고    scopus 로고
    • The question of "partial remedy" has also been discussed by McCormack and Lim (Ref. 14) in their reply to Schlier (Ref. 13)
    • The question of "partial remedy" has also been discussed by McCormack and Lim (Ref. 14) in their reply to Schlier (Ref. 13).
  • 32
    • 85033059006 scopus 로고    scopus 로고
    • note
    • Note that Guo et al. have incorrectly stated [Eqs. (2) and (3) of Ref. 15] that the correspondence principle implies that the classical and quantum results are in agreement. Textbooks that discuss the quantal-classical correspondence assume that the quantum numbers are large so that the difference of 1/2 (in units of ℏω) can be neglected. If the system has a high energy content this is the right classical limit of the quantum case. At very low energies, which are the subject of their paper, this statement is incorrect.
  • 36
    • 36549091743 scopus 로고
    • One can argue that quantum mechanically dissociation is still possible by tunneling. That is in principle correct but the required time scale is not what one would estimate by allowing the molecule to move classically using its zpe to overcome the barrier, except if there are partial barriers to the energy transfer [M. J. Davis and S. K. Gray, J. Chem. Phys. 84, 5389 (1986).
    • (1986) J. Chem. Phys. , vol.84 , pp. 5389
    • Davis, M.J.1    Gray, S.K.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.