Temperature mobility of isomeric cluster equilibria: maximizing the effects in the (CO 2) −2(g) isomeric system

Abstract

Theoretical studies indicate that isomerism in molecular clusters is a typical feature of the species, having substantial effects on their thermodynamics and particularly on the heat capacity term. The latter term can be enhanced considerably by isomeric interplay, especially if fast temperature interchange of relative stability of the isomeric structures takes place. Using the example of the (CO 2) 2 −(g) isomeric cluster system, it is shown how the overall heat capacity enhancement can be maximized with respect to the isomeric energy separation. It is shown that the maximum enhancement amounts to about 136 J K −1 mol −1 for an energy separation of about 53 kJ mol −1.