Strahlungslose Stoßprozesse bei kleinen Geschwindigkeiten

Abstract

Straltlzcnyslose Stopproxesse 6ei kleinezi Gesch'wiut digkeiten VonPhilip1M.Morse z o~d B. C. G . 8 t u e c b e Z b e r g 1 ) (Hit 13 Figuren) Unelastische StoBe zwischert Molekiilen und Molekulen, Xolekiilen und Elektronen, Nolekulen und Ionen verden nach einer Methode behanclelt, bei der die Bewegung der Komponenten in ihrem gegenseitigen Kraftfeld berucksichtigt wird. Die Resultate werden mit den experimentellen Tatsachen beirii Elektronenstofi uncl bei StoBen zweiter Art verglichen.

Elementary Reactions in the Gas Phase Involving Excited Electronic States.

“…What is referred to here is the principle that the exchange of energy accompanying these reactions is not primarily a mechanical problem of collisions, but that the efficiency of the energy transfer will depend upon the strength of the interactions of the electronic fields of the colliding species. The use of potential-energy curves, which take this electronic interaction into account explicitly, is, however, more than just a more elaborate formulation; their use offers one of the most practical quantitative approaches to the general problem of energy interchange (and chemical reactions) whose basic qualitative formulation was laid down by Franck and Eucken. Potential-energy surfaces have proved useful not only in discussing the mechanism of reactions involving electronically excited species, but also in an understanding of the specific magnitudes of quenching cross-sections (102,141,206) (see Section III B). Potentialenergy surfaces have also been utilized in discussing the interconversion of translational and vibrational energies (18,33,61,88), and further progress in the general field of energy interchange in inelastic collisons, a problem intimately connected xvith the mechanisms of reactions, may well be made by a study of the pertinent potential surfaces in the manner outlined above.…”

“…C02*(3II) + 02(X) -> C0202(triplet) -> C0?0"0(triplet) -*> C02(X) + 0i(X) (140) The other state detected is the X, produced on singlet surfaces via nonlinear complexes: CO*(3 ) + 02(32s ) -> C0202(singlet) -> COÍO 0(singlet) C02(X) + 02*(X) (141) This type of transfer of electronic energy is also found to occur with excited mercury and cadmium atoms on collision with the unsaturated hydrocarbons.…”

The Quantum Mechanics of Chemical Kinetics of Homogeneous Gas-Phase Reactions. III. A Collision Model Approximation for Intramolecular Rearrangements.

“…Professor E. P. Wigner(27) has kindly pointed this out. See also, for example, Kallmann and London (13) and Morse and Stueckelberg(21).…”