Computer graphical and semiclassical approaches to molecular rotations and vibrations

Harter, William G.

doi:10.1016/0167-7977(88)90011-1

Cited by 97 publications

(65 citation statements)

References 46 publications

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“…(25) for the state S y . The energy of the unstable stationary state S x corresponds to the top of the barrier responsible for the inversion doublets (K-doublets) in the upper and lower parts of the J-multiplets [3]. Another barrier appears because of the bifurcation for angular momentum at J > J c .…”

Section: Precessional and Vibrational Motions Of An Rotating Ab 2 Molmentioning

confidence: 99%

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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: Precessional and Vibrational Motions Of An Rotating Ab 2 Molmentioning

confidence: 99%

“…Energy level clustering in molecules is very interesting phenomenon, which has been studied for about twenty years [1,2,3,4]. However the main interest was concentrated on highly symmetrical molecules like tetrahydrides.…”

Section: Introductionmentioning

confidence: 99%

Bifurcation in rotational spectra of nonlinear AB2 molecules

Kozin

Pavlichenkov

1996

The Journal of Chemical Physics

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“…They introduced the classical rotational energy surface (CRES) which proved to be very helpful in understanding the qualitative features of RV spectra of such molecules [6,7]. The results presented in Table I and discussed When higher excitations are taken into account some new phenomena, generally connected with the RV coupling, perturb the clear picture presented above.…”

Section: Rotational Levels For J > 20mentioning

confidence: 86%

“…The large number of classical and semiclassical investigations [6][7][8][9][10][11][12] is a consequence of the fact that, in contrast to the traditional quantum methods, classical mechanics provides means for gathering information about the approximate dynamics in high-J regimes.…”

Section: J Pykamentioning

confidence: 99%

Studies of Rotational-Vibrational Dynamics in Highly Excited HDO Molecule

Pyka

1991

Acta Phys. Pol. A

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“…Of particular importance are the integrable cases of the rigid body problem [9,10], which include the free asymmetric top (Euler top) [1,4,6], the symmetric top in a uniform external gravitational field (Lagrange top) [6,11], and the Kovalevskaya top [6,12]. The theory of rigid body motion also provides the basis for analysis and interpretation of the rotational dynamics and spectra of semi-rigid molecules [2,5,13,14,15,16]. In molecular terms the Euler top is simply a free asymmetric top molecule [5,14,15], the Lagrange top models a symmetric top molecule with a dipole moment in an electric field [15,17], while there does not appear to be an obvious molecular analogue for the Kovalevskaya top.…”

Section: Introductionmentioning

confidence: 99%

Classical Mechanics of Dipolar Asymmetric Top Molecules in Collinear Static Electric and Nonresonant Linearly Polarized Laser Fields: Energy-Momentum Diagrams, Bifurcations and Accessible Configuration Space

Arango

Ezra

2008

Int. J. Bifurcation Chaos

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We study classical energy-momentum (E-m) diagrams for rotational motion of dipolar asymmetric top molecules in strong external fields. Static electric fields, nonresonant linearly polarized laser fields, and collinear combinations of the two are investigated. We treat specifically the molecules iodobenzene (a nearly prolate asymmetric top), pyridazine (nearly oblate asymmetric top), and iodopentafluorobenzene (intermediate case). The location of relative equilibria in the E-m plane and associated bifurcations are determined by straightforward calculation, with analytical results given where possible. In cases where analytical solutions cannot be obtained, we resort to numerical solutions, while keeping a geometrical picture of the nature of the solutions to the fore. The classification we obtain of the topology of classically allowed rotor configuration space regions in the E-m diagram is of potential use in characterization of energy eigenstates of the corresponding quantum mechanical problem.

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Computer graphical and semiclassical approaches to molecular rotations and vibrations

Cited by 97 publications

References 46 publications

Bifurcation in rotational spectra of nonlinear AB2 molecules

Bifurcation in rotational spectra of nonlinear AB2 molecules

Studies of Rotational-Vibrational Dynamics in Highly Excited HDO Molecule

Classical Mechanics of Dipolar Asymmetric Top Molecules in Collinear Static Electric and Nonresonant Linearly Polarized Laser Fields: Energy-Momentum Diagrams, Bifurcations and Accessible Configuration Space

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