Examples of compensation that fall into these three cat-egories are defined as secondary, in that they are betterexplained either in terms of well-known thermodynamiclaws (1, 2) or by which systems were selected and whichmeasurements were made (3). In contrast, extra-thermody-namic compensation is defined here as a linear relationshipbetween ⌬H and ⌬S, which does not fall into the thirdcategory above. The key quantity provided by such a rela-tionship is the slope, which defines a compensation tem-perature Tc ⳱ d⌬H/d⌬S. The implication (or hope) isthat for extra-thermodynamic compensation, Tc should re-veal some mechanistic or extra-thermodynamic informationabout the system that cannot be a priori deduced from thelaws of statistical thermodynamics. Examples might be in-formation about the shape of the potential energy surface,the distribution of energy levels available to the system, orthe interaction between different components of the system.
Examples of compensation that fall into these three cat-egories are defined as secondary, in that they are betterexplained either in terms of well-known thermodynamiclaws (1, 2) or by which systems were selected and whichmeasurements were made (3). In contrast, extra-thermody-namic compensation is defined here as a linear relationshipbetween ⌬H and ⌬S, which does not fall into the thirdcategory above. The key quantity provided by such a rela-tionship is the slope, which defines a compensation tem-perature Tc ⳱ d⌬H/d⌬S. The implication (or hope) isthat for extra-thermodynamic compensation, Tc should re-veal some mechanistic or extra-thermodynamic informationabout the system that cannot be a priori deduced from thelaws of statistical thermodynamics. Examples might be in-formation about the shape of the potential energy surface,the distribution of energy levels available to the system, orthe interaction between different components of the system.
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