A periodic orbit analysis of the vibrationally highly excited LiNC/LiCN: A comparison with quantum mechanics

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Articles you may be interested inControl scheme of nonadiabatic transitions with the dynamical shift of potential curve crossing Avoided crossings, conical intersections, and low-lying excited states with a single reference method: The restricted active space spin-flip configuration interaction approach J. Chem. Phys. 137, 084105 (2012); 10.1063/1.4747341Improved results for the excited states of nitric oxide, including the B ∕ C avoided crossingThe correlation diagram of the LiNC/LiCN isomerizing system as a function of ប, taken as a parameter, is considered in conditions of widespread classical chaos. Two series of isolated avoided crossings of very different nature, involving states related by the same 1:8 quantum resonance condition, are characterized and the corresponding interaction matrix elements between adiabatic states analytically calculated and analyzed. One of these series has been found to separate two distinct regions: one for smaller values of ប ͑at any given energy͒ corresponding to regular states, i.e., with a definite nodal pattern, and the other of much more stochastic behavior. Moreover, the effect of the interaction involved in these avoided crossings is to mix the regular wave functions giving rise to wave functions strongly scarred by the periodic orbits of the associated 1:8 classical resonance. This result constitutes an interpretation of the scarring effect from a new perspective.

Section: Introductionmentioning

confidence: 99%

Avoided crossings, scars, and transition to chaos

Arranz

Borondo

Benito

1997

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“…Semiclassical quantization schemes of the classical dynamics have been used with success in several instances. [24][25][26][27][28] They are all based on a careful study of the classical mechanics of the scattering or bound systems, as well as periodic orbit quantization. The scattering systems are subjected to a semiclassical quantization in a manner analogous-though not fully equivalent-to the semiclassical quantization of energy levels for bound systems.…”

Section: Introductionmentioning

confidence: 99%

A quantum and semiclassical study of dynamical resonances in the C+NO→CN+O reaction

Abrol

Wiesenfeld

Lambert

et al. 2001

Accurate quantum mechanical reactive scattering calculations were performed for the collinear CϩNO→CNϩO reaction using a polynomial-modified London Eyring Polanyi Sato ͑PQLEPS͒ potential energy surface ͑PES͒, which has a 4.26 eV deep well in the strong interaction region, and a reference LEPS PES, which has no well in that region. The reaction probabilities obtained for both PESs show signatures for resonances. These resonances were characterized by calculating the eigenvalues and eigenvectors of the collision lifetime matrix as a function of energy. Many resonances were found for scattering on both PESs, indicating that the potential well in the PQLEPS PES does not play the sole role in producing resonances in this relatively heavy atom system and that Feshbach processes occur for both PESs. However, the well in the PQLEPS PES is responsible for the differences in the energies, lifetimes, and compositions of the corresponding resonance states. These resonances are also interpreted in terms of simple periodic orbits supported by both PESs ͑using the WKB formalism͒, to further illustrate the role played by that potential well on the dynamics of this reaction. The existence of the resonances is associated with the dynamics of the long-lived CNO complex, which is much different than that of systems having an activation barrier. Although these results were obtained for a collinear model of the reaction, its collinearly-dominated nature suggests that related resonant behavior may occur in the real world.

“…Many authors [37][38][39][40][41] compared the quantum and classical dynamics to understand the vibrational wave functions and proved the benefit of the classical analyses. Although the periodic orbit analysis is one of the most common and powerful tool, we adopted the Poincarè SOS, taking advantage of the 2D model, in order to characterize 2D trajectories.…”

Section: Two-dimensional Analysesmentioning

confidence: 99%

Regularity in highly excited vibrational dynamics of NOCl (X 1A′): Quantum mechanical calculations on a new potential energy surface

Yamashita

Kato

2003

Calculation of the structure, potential energy surface, vibrational dynamics, and electric dipole properties for the Xe:HI van der Waals complex Ab initio potential energy surfaces, total absorption cross sections, and product quantum state distributions for the low-lying electronic states of N 2 O A new potential energy surface ͑PES͒ of NOCl in the ground electronic state (X 1 AЈ) is constructed based on multireference configuration interaction calculations. Almost all the vibrational eigenstates up to the dissociation threshold are obtained using filter diagonalization method with the present PES. The vibrational excitation energies are in good agreement with the experimental values. The nearest neighbor level spacing distribution shows that the vibrational structure is regarded as regular up to the dissociation threshold. The distribution of radiative coupling elements also supports the regularity. It is further found out that the NO stretching mode is strongly decoupled from the other modes. Taking advantage of this result, the two-dimensional ͑2D͒ analyses are carried out with the NO distance fixed. The 2D wave functions have clear nodal patterns even near the dissociation threshold, indicating that the 2D quantum dynamics is regular as in the three-dimensional case. Comparing the 2D classical dynamics with the 2D wave functions, quasiperiodic trajectories closely related to the corresponding quantum dynamics are extracted. Although it is generally believed that the phase space becomes fully chaotic with approaching to the dissociation threshold, two stable islands of regular motion still remain even at this energy region.