44 research outputs found
On inelastic hydrogen atom collisions in stellar atmospheres
The influence of inelastic hydrogen atom collisions on non-LTE spectral line
formation has been, and remains to be, a significant source of uncertainty for
stellar abundance analyses, due to the difficulty in obtaining accurate data
for low-energy atomic collisions either experimentally or theoretically. For
lack of a better alternative, the classical "Drawin formula" is often used.
Over recent decades, our understanding of these collisions has improved
markedly, predominantly through a number of detailed quantum mechanical
calculations. In this paper, the Drawin formula is compared with the quantum
mechanical calculations both in terms of the underlying physics and the
resulting rate coefficients. It is shown that the Drawin formula does not
contain the essential physics behind direct excitation by H atom collisions,
the important physical mechanism being quantum mechanical in character.
Quantitatively, the Drawin formula compares poorly with the results of the
available quantum mechanical calculations, usually significantly overestimating
the collision rates by amounts that vary markedly between transitions.Comment: 9 pages, 6 figures, accepted for A&
Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Comparison
Knowledge of the relative stabilities of alane (AlH3) complexes with electron
donors is essential for identifying hydrogen storage materials for vehicular
applications that can be regenerated by off-board methods; however, almost no
thermodynamic data are available to make this assessment. To fill this gap, we
employed the G4(MP2) method to determine heats of formation, entropies, and
Gibbs free energies of formation for thirty-eight alane complexes with NH3-nRn
(R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA),
quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran
(THF). Monomer, bis, and selected dimer complex geometries were considered.
Using these data, we computed the thermodynamics of the key formation and
dehydrogenation reactions that would occur during hydrogen delivery and alane
regeneration, from which trends in complex stability were identified. These
predictions were tested by synthesizing six amine-alane complexes involving
trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and
hexamine, and obtaining upper limits of delta G for their formation from
metallic aluminum. Combining these computational and experimental results, we
establish a criterion for complex stability relevant to hydrogen storage that
can be used to assess potential ligands prior to attempting synthesis of the
alane complex. Based on this, we conclude that only a subset of the tertiary
amine complexes considered and none of the ether complexes can be successfully
formed by direct reaction with aluminum and regenerated in an alane-based
hydrogen storage system.Comment: Accepted by the Journal of Physical Chemistry
The rovibrational spectrum of BeH, MgH and CaH at high temperatures in the state: a theoretical study
Accurate line lists for three molecules, BeH, MgH and CaH, in their ground
electronic states are presented. These line lists are suitable for temperatures
relevant to exoplanetary atmospheres and cool stars (up to 2000K). A
combination of empirical and \textit{ab initio} methods is used. The
rovibrational energy levels of BeH, MgH and CaH are computed using the programs
Level and DPotFit in conjunction with `spectroscopic' potential energy curves
(PECs). The PEC of BeH is taken from the literature, while the PECs of CaH and
MgH are generated by fitting to the experimental transition energy levels. Both
spin-rotation interactions (except for BeH, for which it is negligible) and
non-adiabatic corrections are explicitly taken into account. Accurate line
intensities are generated using newly computed \textit{ab initio} dipole moment
curves for each molecule using high levels of theory. Full line lists of
rotation-vibration transitions for BeH, MgH, MgH, MgH
and CaH are made available in an electronic form as supplementary data
to this article and at \url{www.exomol.com}.Comment: MNRAS (in press
ChemInform Abstract: G2 Molecular Orbital Investigation of H4AlXH3+ (X: N, P, and As) and H4AlYH2+ (Y: O, S, and Se) Interactions.
Etude theorique de la surface de potentiel du systeme HO2 + H : influence de la correlation electronique
SIGLECNRS T Bordereau / INIST-CNRS - Institut de l'Information Scientifique et TechniqueFRFranc
A Theoretical investigation of furan-AlX3, pyrrole-AlX3 and thiophene-AlX3 (X = H, F, Cl, Br) interactions
X3Al-YC4H4 (X = H, F, Cl and Br; Y = O in furan, Y=NH in pyrrole, and Y = S in thiophen) have been investigated as donorâacceptor complex types using the DFT level of theory. Both staggered and eclipsed conformations have been examined. For all complexes, the first one is found to be favored. The DFT results including the BSSE contribution show that fluoro complexes are more stable than the others. The interaction diagrams prove that the evolution of complexation energy depends on the coordination mode. In fact, this is a simple âHOMOâLUMOâ interaction for X3Al-YC4H4 complexes. This quantum chemistry analysis of the X3Al-YC4H4 donorâacceptor complexes shows no correlation with the charge transfer.<br /