59 research outputs found
Long range intermolecular forces in triatomic systems: connecting the atom-diatom and atom-atom-atom representations
The long-range forces that act between three atoms are analysed in both
atom-diatom and atom-atom-atom representations. Expressions for atom-diatom
dispersion coefficients are obtained in terms of 3-body nonadditive
coefficients. The anisotropy of atom-diatom C_6 dispersion coefficients arises
primarily from nonadditive triple-dipole and quadruple-dipole forces, while
pairwise-additive forces and nonadditive triple-dipole and
dipole-dipole-quadrupole forces contribute significantly to atom-diatom C_8
coefficients. The resulting expressions are applied to dispersion coefficients
for Li + Li_2 (triplet) and recommendations are made for the best way to obtain
global triatomic potentials that dissociate correctly both to three separated
atoms and to an atom and a diatomic molecule.Comment: To be published in a special issue of Molecular Physics in honour of
Mark Chil
Near-dissociation states and coupled potential curves for the HeN+ complex
The near-dissociation microwave rovibronic spectra of HeN+ [Carrington et al., Chem. Phys. Lett. 262, 598 (1996)] are used to obtain coupled potential energy curves for the six electronic states correlating with He+N+ 3P0, 3P1, and 3P2. High-quality ab initio calculations are carried out, using a spin-restricted open-shell coupled-cluster method with an augmented correlation-consistent quintuple-zeta basis set (aug-cc-pV5Z). Fully coupled calculations of bound and quasibound states are performed, including all six electronic states, and suggest two possible assignments of the observed transitions. The potentials are then morphed (scaled) to reproduce the experimental frequencies. One of the two assignments, designated SH1, is preferred because it gives a more satisfactory explanation of the observed hyperfine splittings. The corresponding morphed potential has well depths of 1954 cm−1 and 192 cm−1 for the spin-free 3Σ− and 3Π curves, respectively
Spectroscopy of Na<sup>+</sup>·Rg and transport coefficients of Na<sup>+</sup> in Rg (Rg=He-Rn)
High-level ab initio calculations are used to obtain accurate potential energy curves for Na+·Kr, Na+·Xe, and Na+·Rn. These data are used to calculate spectroscopic parameters for these three species, and the data for the whole Na+·Rg series (Rg=He-Rn) are compared. Potentials for the whole series are then used to calculate both mobilities and diffusion coefficients for Na+ moving through a bath of each of the six rare gases, under conditions that match previous experimental determinations. Different available potentials and experimental data are then statistically compared. It is concluded that the present potentials are very accurate. The potential and other data for Na+·Rn appear to be the first such reported
On the long-range and short-range behavior of potentials from reproducing kernel Hilbert space interpolation
Feshbach resonances in ultracold atom-molecule collisions
We investigate the presence of Feshbach resonances in ultracold
alkali-dialkali reactive collisions. Quantum scattering calculations are
performed on a new Na_3 quartet potential energy surface. An analysis of
scattering features is performed through a systematic variation of the
nonadditive three-body interaction potential. Our results should provide useful
information for interpreting future atom-molecule collision experiments.Comment: 7 pages, 6 figure
Cold collisions of OH and Rb. I: the free collision
We have calculated elastic and state-resolved inelastic cross sections for
cold and ultracold collisions in the Rb() + OH() system,
including fine-structure and hyperfine effects. We have developed a new set of
five potential energy surfaces for Rb-OH() from high-level {\em ab
initio} electronic structure calculations, which exhibit conical intersections
between covalent and ion-pair states. The surfaces are transformed to a
quasidiabatic representation. The collision problem is expanded in a set of
channels suitable for handling the system in the presence of electric and/or
magnetic fields, although we consider the zero-field limit in this work.
Because of the large number of scattering channels involved, we propose and
make use of suitable approximations. To account for the hyperfine structure of
both collision partners in the short-range region we develop a
frame-transformation procedure which includes most of the hyperfine
Hamiltonian. Scattering cross sections on the order of cm are
predicted for temperatures typical of Stark decelerators. We also conclude that
spin orientation of the partners is completely disrupted during the collision.
Implications for both sympathetic cooling of OH molecules in an environment of
ultracold Rb atoms and experimental observability of the collisions are
discussed.Comment: 20 pages, 16 figure
Interactions and dynamics in Li+Li2 ultracold collisions
A potential energy surface for the lowest quartet electronic state (A′4) of lithium trimer is developed and used to study spin-polarized Li+Li2collisions at ultralow kinetic energies. The potential energy surface allows barrierless atom exchange reactions. Elastic and inelastic cross sections are calculated for collisions involving a variety of rovibrational states of Li2. Inelastic collisions are responsible for trap loss in molecule production experiments. Isotope effects and the sensitivity of the results to details of the potential energy surface are investigated. It is found that for vibrationally excited states, the cross sections are only quite weakly dependent on details of the potential energy surface
Three-body non-additive forces between spin-polarized alkali atoms
Three-body non-additive forces in systems of three spin-polarized alkali
atoms (Li, Na, K, Rb and Cs) are investigated using high-level ab initio
calculations. The non-additive forces are found to be large, especially near
the equilateral equilibrium geometries. For Li, they increase the three-atom
potential well depth by a factor of 4 and reduce the equilibrium interatomic
distance by 0.9 A. The non-additive forces originate principally from chemical
bonding arising from sp mixing effects.Comment: 4 pages, 3 figures (in 5 files
Spectroscopy of Na+⋅Rg and transport coefficients of Na+ in Rg(Rg=He–Rn)
High-level ab initio calculations are used to obtain accurate potential energy curves for Na+·Kr, Na+·Xe, and Na+·Rn. These data are used to calculate spectroscopic parameters for these three species, and the data for the whole Na+·Rg series (Rg=He-Rn) are compared. Potentials for the whole series are then used to calculate both mobilities and diffusion coefficients for Na+ moving through a bath of each of the six rare gases, under conditions that match previous experimental determinations. Different available potentials and experimental data are then statistically compared. It is concluded that the present potentials are very accurate. The potential and other data for Na+·Rn appear to be the first such reported
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