English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Zendy Open

Presents the pdf analysis as premium feature

PDF Analysis

Insights

Presents the summarisation as premium feature

Summarisation

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the zaia usage as premium feature

ZAIA

Zendy Tools

Zendy Plus

Presents the access of premium content as premium feature

Premium Content

In its usual form activated complex theory assumes a quasiequilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced. The new equation for the transmission coefficient contains internal centrifugal terms. The fourth assumption can also be weakened and a rotational interaction included in the formalism. In applications of the rate equation use can be made of the recent finding that in the immediate vicinity of a saddle point or a minimum, a potential energy surface can be imitated in some major topographical respects by a surface permitting separation of variables. The separated wave equation for the reaction coordinate is then curvilinear because of the usual curvature of the path of steepest ascent to the saddle point. Calculations of transmission coefficients and rates can be made and compared with those obtainable from the usual one‐dimensional Cartesian‐like calculations on the one hand and with some based on the numerical integration of the n‐dimensional Schrodinger equation on the other. An application to a common three‐center problem is discussed.

Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment