Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. II. Normal to local mode transition and quantum stochasticity

Abstract

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The Vibrational Level Spectrum of H2O(X̃1A′) on a Partridge–Schwenke Potential up to the Dissociation Limit

“…One can, for example, symmetrize the radial Radau coordinates (r ± = (r 1 ± r 2 )/ √ 2) to block diagonalize the Hamiltonian matrix (27 ). However, singularities in the rotational constant B(r 1 , r 2 ) may arise at r 1,2 = 0.…”

High order finite difference algorithms for solving the Schrödinger equation in molecular dynamics. II. Periodic variables

“…III we study a real triatomic molecule, the sulfur dioxide, using a spectroscopic potential in Jacobi coordinates. 13 Vibrational levels of SO 2 have been calculated by Guo and co-workers up to 4 eV above the zero-point energy ͑ZPE͒ [14][15][16] with filter diagonalization techniques [17][18][19] and DVR for the Hamiltonian. We do not compute accurate vibrational eigenenergies but we investigate the stability in time evolution of initial Gaussian wave packets.…”

“…Recently, extended threedimensional quantum mechanical calculations for the vibrational levels of this molecule were carried out by Guo and co-workers [14][15][16] using the spectroscopic potential of Kauppi and Halonen. 13 The potential is expressed in terms of the bend angle and Morse radial variables and reproduces the experimentally observed vibrational levels up to high energies.…”

“…Statistical analysis of the energy level spacing distributions showed largely regular behavior. 15,[28][29][30][31] The purpose of our calculations is not to reproduce the eigenvalues of Ma and Guo 15 but instead to propagate in time wave packets on the same potential function for testing the accuracy and stability of FD methods described in the previous section. Thus, we solve the time-dependent Schrö-dinger equation…”

Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. III. Emission spectra from the C̃ 1B2 state

“…Recently, efforts have been devoted in our group to study the highly excited vibrational spectrum of SO 2 (X ), 21,22 motivated by the abundance of experimental and theoretical data on this system. Approximately 4700 vibrational levels below 25 000 cm Ϫ1 were determined on an empirical PES using a Chebyshev-based filter-diagonalization ͑FD͒ method.…”