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Critical phenomena

 
Sci-Tech Dictionary: critical phenomena
(′krid·ə·kəl fə′näm·ə·nə)

(physical chemistry) Physical properties of liquids and gases at the critical point (conditions at which two phases are just about to become one); for example, critical pressure is that needed to condense a gas at the critical temperature, and above the critical temperature the gas cannot be liquefied at any pressure.


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Sci-Tech Encyclopedia: Critical phenomena
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The unusual physical properties displayed by substances near their critical points. The study of critical phenomena of different substances is directed toward a common theory.

Ideally, if a certain amount of water (H2O) is sealed inside a transparent cell and heated to a high temperature T, for instance, T > 647 K (374°C or 705°F), the enclosed water exists as a transparent homogeneous substance. When the cell is allowed to cool down gradually and reaches a particular temperature, namely the boiling point, the enclosed water will go through a phase transition and separate into liquid and vapor phases. The liquid phase, being more dense, will settle into the bottom half of the cell. This sequence of events takes place for water at most moderate densities. However, if the enclosed water is at a density close to 322.2 kg · m−3, rather extraordinary phenomena will be observed. As the cell is cooled toward 647 K (374°C or 705°F), the originally transparent water will become increasingly turbid and milky, indicating that visible light is being strongly scattered. Upon slight additional cooling, the turbidity disappears and two clear phases, water and vapor, are found. This phenomenon is called the critical opalescence, and the water sample is said to have gone through the critical phase transition. The density, temperature, and pressure at which this transition happens determine the critical point and are called respectively the critical density ρc, the critical temperature Tc, and the critical pressure Pc. For water ρc = 322.2 kg · m−3, Tc = 647 K (374°C or 705°F), and Pc = 2.21 × 107 pascals. See also Opalescence.

Different fluids, as expected, have different critical points. Although the critical point is the end point of the vapor pressure curve on the pressure-temperature (P-T) plane (see illustration), the critical phase transition is qualitatively different from that of the ordinary boiling phenomenon that happens along the vapor pressure curve. In addition to the critical opalescence, there are other highly unusual phenomena that are manifested near the critical point; for example, both the isothermal compressibility and heat capacity diverge to infinity as the fluid approaches Tc.

Phase diagram of water (H<sub>2</sub>O) on pressure-temperature (<i>P-T</i>) plane.
Phase diagram of water (H2O) on pressure-temperature (P-T) plane.

Many other systems, for example, ferromagnetic materials such as iron and nickel, also have critical points. The ferromagnetic critical point is also known as the Curie point. As in the case of fluids, a number of unusual phenomena take place near the critical point of ferromagnets, including singular heat capacity and divergent magnetic susceptibility. The study of critical phenomena is directed toward describing the various anomalous and interesting types of behavior near the critical points of these diverse and different systems with a single common theory. See also Curie temperature; Ferromagnetism.


Wikipedia: Critical phenomena
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In physics, critical phenomena is the collective name associated with the physics of critical points. Most of them stem from the divergence of the correlation length. Critical phenomena include scaling relations among different quantities, power-law divergences of some quantities (such as the magnetic susceptibility in the ferromagnetic phase transition) described by critical exponents, universality, fractal behaviour, ergodicity breaking. Critical phenomena take place in second order phase transition, although not exclusively.

The critical behavior is usually different from the mean-field approximation which is valid away from the phase transition, since the latter neglects correlations, which become increasingly important as the system approaches the critical point where the correlation length diverges. Many properties of the critical behavior of a system can be derived in the framework of the renormalization group.

In order to explain the physical origin of these phenomena, we shall use the Ising model as a pedagogical example.

Contents

The critical point of the 2D Ising model

Let us consider a 2D square array of classical spins which may only take two positions: +1 and −1, at a certain temperature T, interacting through the Ising classical Hamiltonian:

H= -J \sum_{[i,j]} S_i\cdot S_j

where the sum is extended over the pairs of nearest neighbours and J is a coupling constant, which we will consider to be fixed. There is a certain temperature, called the Curie temperature or critical temperature, Tc below which the system presents ferromagnetic long range order. Above it, it is paramagnetic and is apparently disordered.

At temperature zero, the system may only take one global sign, either +1 or -1. At higher temperatures, but below Tc, the state is still globally magnetized, but clusters of the opposite sign appears. As the temperature increases, these clusters start to contain smaller clusters themselves, in a typical Russian dolls picture. Their typical size, called the correlation length, ξ grows with temperature until it diverges at Tc. This means that the whole system is such a cluster, and there is no global magnetization. Above that temperature, the system is globally disordered, but with ordered clusters within it, whose size is again called correlation length, but it is now decreasing with temperature. At infinite temperature, it is again zero, with the system fully disordered.

Divergences at the critical point

The correlation length diverges at the critical point: as T\to T_c, \xi\to\infty. This divergence poses no physical problem. Other physical observables diverge at this point, leading to some confusion at the beginning.

The most important is susceptibility. Let us apply a very small magnetic field to the system in the critical point. A very small magnetic field is not able to magnetize a large coherent cluster, but with these fractal clusters the picture changes. It affects easily the smallest size clusters, since they have a nearly paramagnetic behaviour. But this change, in its turn, affects the next-scale clusters, and the perturbation climbs the ladder until the whole system changes radically. Thus, critical systems are very sensitive to small changes in the environment.

Other observables, such as the specific heat, may also diverge at this point. All these divergences stem from that of the correlation length.

Critical exponents and universality

As we approach the critical point, these diverging observables behave as A(T)\approx (T-T_c)^\alpha for some exponent α. These exponents are called critical exponents and are robust observables. Even more, they take the same values for very different physical systems. This intriguing phenomenon, called universality, is explained successfully by the renormalization group.

Critical dynamics

Critical phenomena may also appear for dynamic quantities, not only for static ones. In fact, the divergence of the characteristic time τ of a system is directly related to the divergence of the thermal correlation length ξ by the introduction of a dynamical exponent z and the relation \tau =\xi^{\,z}. The voluminous static universality class of a system splits into different, less voluminous dynamic universality classes with different values of z but a common static critical behaviour.

Ergodicity breaking

Ergodicity is the assumption that a system, at a given temperature, explores the full phase space, just each state takes different probabilities. In an Ising ferromagnet below Tc this does not happen. If T < Tc, never mind how close they are, the system has chosen a global magnetization, and the phase space is divided into two regions. From one of them it is impossible to reach the other, unless a magnetic field is applied, or temperature is raised above Tc.

See also superselection sector

Mathematical tools

The main mathematical tools to study critical points are renormalization group, which takes advantage of the Russian dolls picture to explain universality and predict numerically the critical exponents, and Variational perturbation theory, which converts divergent perturbation expansions into convergent strong-coupling expansions relevant to critical phenomena. In two-dimensional systems, Conformal field theory is a powerful tool which has discovered many new properties of 2D critical systems, employing the fact that scale invariance, along with a few other requisites, leads to an infinite symmetry group.

See also

Bibliography

  • Phase Transitions and Critical Phenomena, vol. 1-20 (1972-2001), Academic Press, Ed.: C. Domb, M.S. Green, J.L. Lebowitz
  • J.J. Binney et al. (1993): The theory of critical phenomena, Clarendon press.
  • N. Goldenfeld (1993): Lectures on phase transitions and the renormalization group, Addison-Wesley.
  • H. Kleinert and V. Schulte-Frohlinde, Critical Properties of φ4-Theories, World Scientific (Singapore, 2001); Paperback ISBN 981-02-4659-5 (Read online at [1])
  • J. M. Yeomans, Statistical Mechanics of Phase Transitions (Oxford Science Publications, 1992) ISBN 0198517300
  • M.E. Fisher, Renormalization Group in Theory of Critical Behavior, Reviews of Modern Physics, vol. 46, p. 597-616 (1974)

 
 

 

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