Potential energy surfaces have been calculated for the four lowest electronic states of Na (3 2S, 3 2P)+H2(1Σ+g) by means of the RHF–SCF and PNO–CEPA methods. For the so‐called quenching process of Na (3 2P) by H2 at low initial translational energies (E–VRT energy transfer) the energetically most favorable path occurs in C2v symmetry, since—at intermediate Na–H2 separation—the ? 2B2 potential energy surface is attractive. From the CEPA calculations, the crossing point of minimal energy between the ? 2A1 and ? 2B2 surfaces is obtained at Rc = 3.57 a.u. and rc = 2.17 a.u. with an energy difference to the asymptotic limit (R = ∞, r = re) of −0.06 eV. It is thus classically accessible without any initial translational energy, but at low initial translational energies (∼0.1 eV) quenching will be efficient only for arrangements of collision partners close to C2v symmetry. There is little indication of an avoiding crossing with an ionic intermediate correlating asymptotically with Na+ and H2− as was assumed in previous discussions of the quenching process. The dependence of the total quenching cross sections on the initial translational energy is discussed by means of the ’’absorbing sphere’’ model, taking the initial zero‐point vibrational energy of the hydrogen molecule into account. New experimental data of the product channel distribution in H2 for center‐of‐mass forward scattering are presented. The final vibrational states v′ = 3, 2, 1, and 0 of H2 are populated to about 26%, 61%, 13%, and 0%, respectively. The observed distributions in H2 (and D2) may be rationalized by simple dynamic considerations on the basis of the calculated surfaces.
Skip Nav Destination
Article navigation
1 December 1981
Research Article|
December 01 1981
Collisions of excited Na atoms with H2 molecules. I. Ab initio potential energy surfaces and qualitative discussion of the quenching process
Peter Botschwina;
Peter Botschwina
Fachbereich Chemie der Universität Kaiserslautern, D‐6750 Kaiserslautern, Federal Republic of Germany
Search for other works by this author on:
Wilfried Meyer;
Wilfried Meyer
Fachbereich Chemie der Universität Kaiserslautern, D‐6750 Kaiserslautern, Federal Republic of Germany
Search for other works by this author on:
Ingolf V. Hertel;
Ingolf V. Hertel
Fachbereich Physik der Freien Universität Berlin, D‐1000 Berlin 33, Federal Republic of Germany
Search for other works by this author on:
W. Reiland
W. Reiland
Fachbereich Physik der Freien Universität Berlin, D‐1000 Berlin 33, Federal Republic of Germany
Search for other works by this author on:
J. Chem. Phys. 75, 5438–5448 (1981)
Citation
Peter Botschwina, Wilfried Meyer, Ingolf V. Hertel, W. Reiland; Collisions of excited Na atoms with H2 molecules. I. Ab initio potential energy surfaces and qualitative discussion of the quenching process. J. Chem. Phys. 1 December 1981; 75 (11): 5438–5448. https://doi.org/10.1063/1.441945
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Freezing point depression of salt aqueous solutions using the Madrid-2019 model
Cintia P. Lamas, Carlos Vega, et al.
Related Content
Electronic to vibrational rotational energy transfer in collisions of Na(3 2P) with NO and small organic molecules
J. Chem. Phys. (June 1981)
Correlation Energy in Atomic Systems. V. Degeneracy Effects for the Second‐Row Atoms
J. Chem. Phys. (September 1968)
Crossed beam (E–VRT) energy transfer experiment
J. Chem. Phys. (July 1979)
New optical method for studying anisotropic diffusion in liquid crystals
J. Chem. Phys. (November 1974)