Clustering of rovibrational energy levels in the highly excited H<sub>2</sub>S molecule

Pyka, Jan

doi:10.1080/00268979000102591

Cited by 12 publications

(13 citation statements)

References 18 publications

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“…The noticeable softening of the precessional modes in the ground and ν 2 vibrational states of H 2 O and H 2 S was interpreted as a possible bifurcation in this molecules [5,7]. More precise numerical calculations based on the quantum Hamiltonian of the rigid-bender model were carried out soon [8,9]. They demonstrated the formation of fourfold energy clusters for J greater that J c .…”

Section: Introductionmentioning

confidence: 99%

Bifurcation in rotational spectra of nonlinear AB2 molecules

Kozin

Pavlichenkov

1996

The Journal of Chemical Physics

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A classical microscopic theory of rovibrational motion at high angular momenta in symmetrical non-linear molecules AB 2 is derived within the framework of small oscillations near the stationary states of a rotating molecule. The full-dimensional analysis including stretching vibrations has confirmed the existence of the bifurcation predicted previously by means of the rigid-bender model [see B.I. Zhilinskii and I.M. Pavlichenkov, Opt. Spectrosk. (USSR) 64, 413-414 (1988)]. The formation of fourfold energy clusters resulting from the bifurcation has been experimentally verified for H 2 Se and it has been demonstrated in fully-dimensional quantum mechanical calculations carried out with the MORBID computer program.We show in the present work that apart from the level clustering, the bifurcation produces physically important effects including molecular symmetry-breaking and a transition from the normal mode to the local mode limit for the stretching vibrations due to rovibrational interaction. The application of the present theory with realistic molecular potentials to the H 2 Te, H 2 Se and H 2 S hydrides results in predictions of the bifurcation points very close to those calculated previously. However for the lighter H 2 O molecule we find that the bifurcation occurs at higher values of the total angular momentum than obtained in previous estimations. The present work shows it to be very unlikely that the bifurcation in H 2 O will lead to clustering of energy levels. This result is in agreement with recent variational calculations.

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Section: Introductionmentioning

confidence: 99%

Bifurcation in rotational spectra of nonlinear AB2 molecules

Kozin

Pavlichenkov

1996

The Journal of Chemical Physics

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“…Studies of highly excited H2O [16] and H2S [17] molecules are a good illustration of these new possibilities. In both cases the results of calculations enable one to distinguish several dynamical regions depending on the RV coupling and RV correlation.…”

Section: J Pykamentioning

confidence: 99%

“…In high-precision calculations the CI-like variational approach is proposed [13,[15][16][17][18]. The constuction of an SC/orthogonal (SCO) basis-function set is described in [15,16].…”

Section: Solution Of the Bending-rotating Problemmentioning

confidence: 99%

“…The reduced vibrational density matrix Dv (ϑ) and the reduced local angular momentum operation introduced in [15] were already applied with success to the study of the RV dynamics of the H2O [16] and H2 S [17] molecules. Now, for the same purposes, they will be used in the investigation of the HDO molecule described by υ = 0 and J = 40.…”

Section: Dynamics Of the Interacting Rotational And Bending Motionsmentioning

confidence: 99%

“…For given J, we have two blocks depending on the τ value and their dimension is equal to the product of the number of vibrational functions by the number of adequate rotational functions. In the case of C2v molecules such as H2O or H2 S [16,17] the total Hamiltonian matrix could be (with the use of symmetry properties) factorized on four blocks which considerably reduces the numerical work. For HDO molecule we have to deal with matrices twice as large.…”

Section: Solution Of the Bending-rotating Problemmentioning

confidence: 99%

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