A phenomenological equation of state is presented which describes a thermodynamic system having a tricritical point. The equation is an asymptotic one---in the sense of ordinary critical-point theory---which obeys certain scaling relations and is consistent with Griffiths-Wheeler theory. It relates all tricritical exponents to the underlying second-order exponents by introducing a new exponent which determines the geometry of certain first-order phase lines at the tricritical point. The predictions are in reasonable agreement with experimental and numerical results.
The goal of this work is to provide an analysis of spaces of critical points for multicomponent systems. First, we propose the geometric concept of order
O for critical points; we distinguish it from a previous definition of a "multicritical" point. Specifically, we may define the intersection of spaces of critical points of order
O to be a space of critical points of order (
O+1). Ordinary critical points are defined to be of order
O=2, so that the tricritical points introduced by Griffiths are of order
O=3. We discuss more general examples of critical spaces of order
O=3 which are known for a wide variety of systems; we also propose several examples of models of magnetic systems showing critical points of order
O=4---i.e., systems having intersecting lines of tricritical points. The analysis of critical and coexistence spaces also provides a new form of the Gibbs phase rule suitable for complex magnetic models. Next we define---for the critical points of order
O of which examples have been given---special directions in terms of which to make a scaling hypothesis. We give the hypothesis for simple systems and then for tricritical points, and then, in a subsequent paper, part II, the special directions are used to make a scaling hypothesis at spaces of critical points of any order. Certain predictions (e.g., scaling laws and "single-power" scaling functions) follow in a simple and straightforward fashion. We consider the scaling hypothesis at a critical space of order
O in terms of a group of transformations. We can define a set of invariants of the group. It is possible, for $\mathcal{O}\ensuremath{\ge}3$, to make a second scaling hypothesis for the space of order $\mathcal{O}\ensuremath{-}1$ using certain of these invariants as independent variables. This is advantageous because certain "double-power" scaling functions then follow directly; these predict that for
O=3, experimental data collapse from a volume onto a line. This prediction is to be contrasted with ordinary scaling functions, which predict that data collapse by only a single dimension (e.g., from a volume onto a surface or from a surface onto a line).
There are two independent critical exponents that describe the behavior of systems near their critical point. However, at the critical point only the exponent η, which describes the decay of the correlation function, is usually discussed. We emphasize that there is a second independent exponent η′ that describes the decay of the fourth-order correlation function. The exponent η′ is related to the exponents determining the behavior of thermodynamic functions near criticality via a fluctuation-response equation for the specific heat. We also discuss a scaling law for η′.
A semi-microscopic scaling-field theory is developed for crossover phenomena near critical and tricritical points. The theory is based on a renormalization-group description of a model with two competing fixed points (such as a critical and a tricritical fixed point) in terms of scaling fields. The coupled nonlinear differential equations for scaling fields are truncated such as to preserve the physics essential for crossover phenomena. The approach allows the explicit calculation of thermodynamic functions for (i) tricritical systems and (ii) critical systems with an irrelevant scaling field. We obtain, for example, an explicit expression for the scaling function of the susceptibility, which describes the crossover from the tricritical to the critical region. The idea of "flow diagrams" in the scaling-field space is used to characterize crossover phenomena globally in the whole critical region. The concept of asymptotic critical exponents is generalized and effective critical exponents are introduced as logarithmic derivatives of thermodynamic quantities with respect to experimental fields and scaling fields, respectively. By using the method of effective exponents the size of the crossover region between regions of different asymptotic critical behavior is estimated. For the susceptibility, the width of the crossover region in decades of the effective temperature variable is roughly equal to the inverse of the crossover exponent. In the case of a critical system with a slow transient the asymptotic critical exponent is only reached extremely close to the critical point (unless the amplitude of the transient vanishes). It might then be impossible to determine the asymptotic exponent experimentally or by conventional series-expansion techniques, and an analysis of the data in terms of effective exponents is the alternative. The scaling-field approach is applied to three systems with crossover phenomena: (i) the model for tricritical systems with molecular-field tricritical exponents, (ii) the Ashkin-Teller model in three dimensions, and (iii) a model for phase transitions with Fisher exponent renormalization due to a constraint.