Linear response theory examples

Linear response theory is an example of a microscopic approach to the foundations of non-equilibrium thennodynamics. It requires knowledge of tire Hamiltonian for the underlying microscopic description. In principle, it produces explicit fomuilae for the relaxation parameters that make up the Onsager coefficients. In reality, these expressions are extremely difficult to evaluate and approximation methods are necessary. Nevertheless, they provide a deeper insight into the physics. 

The paper is organized as follows. In Section 2, derivation of the the SRPA formalism is done. Relations of SRPA with other alternative approaches are commented. In Sec. 3, the method to calculate SRPA strength function (counterpart of the linear response theory) is outlined. In Section 4, the particular SRPA versions for the electronic Kohn-Sham and nuclear Skyrme functionals are specified and the origin and role of time-odd currents in functionals are scrutinized. In Sec. 5, the practical SRPA realization is discussed. Some examples demonstrating accuracy of the method in atomic clusters and nuclei are presented. The summary is done in Sec. 6. In Appendix A, densities and currents for Skyrme functional are listed. In Appendix B, the optimal ways to calculate SRPA basic values are discussed. 

The paper [50] was written, when our general linear response-theory (ACF method) was still in progress, so the derivation of the spectral function described in Ref. 50 is more specialized than that given, for example, in VIG and GT. 

Here, G(t) is the quantum autocorrelation function (ACF) of the dipole moment operator responsible for the dipolar absorption transition, whereas oo is the angular frequency and t is the time. Equation (1) has been used, for example, by Bratos [45] and Robertson and Yarwood [46] in their semiclassical studies of H-bonded species within the linear response theory. 

However, from the point of view of linear response theory, the definitions (174) or (178) suffer from several drawbacks. Actually, the function X ( , tw) as defined by Eq. (174) is not the Fourier transform of the function X (, x), but a partial Fourier transform computed in the restricted time interval 0 < x < tw. As a consequence, it does not possess the same analyticity properties as the generalized susceptibility x( ) defined by Eq. (179). While the latter, extended to complex values of co, is analytic in the upper complex half-plane (Smoo > 0), the function Xi ( - tw) is analytic in the whole complex plane. As a very simple example, consider the exponentially decreasing response function... 

In this section we develop a general linear response theory for which the coupling of the system to the field in Eqs. [91] is small [i.e., fjt) 1]. Linear response theory should, in general, take into account the possibility of phase space compression coming from either the coupling to the external field or from the extended phase space variables. In traditional formulations of linear response theory, phase space compression has not been carefully considered. The present formulation treats the first level of compressibility exactly, for example, the compressibility due to the presence of an extended system (such as ther-... 

Here y = x/r[ = =C, /2/IkT is chosen as the inertial effects parameter (y = /2/y is effectively the inverse square root of the parameter y used earlier in Section I). Noting e initial condition, Eq. (134), all the < (()) in Eq. (136) will vanish with the exception of n = 0. Furthermore, Eq. (136) is an example of hoyv, using the Laplace integration theorem above, all recurrence relations associated with the Brownian motion may be generalized to fractional dynamics. The normalized complex susceptibility /(m) = x ( ) z"( ) is given by linear response theory as... 

Equilibrium statistical mechanics is a first principle theory whose fundamental statements are general and independent of the details associated with individual systems. No such general theory exists for nonequilibrium systems and for this reason we often have to resort to ad hoc descriptions, often of phenomenological nature, as demonstrated by several examples in Chapters 1 and 8. Equilibrium statistical mechanics can however be extended to describe small deviations from equilibrium in a way that preserves its general nature. The result is Linear Response Theory, a statistical mechanical perturbative expansion about equilibrium. In a standard application we start with a system in thermal equilibrium and attempt to quantify its response to an applied (static- or time-dependent) perturbation. The latter is assumed small, allowing us to keep only linear terms in a perturbative expansion. This leads to a linear relationship between this perturbation and the resulting response. 

The notation A = iLA, A = (iL)M,... recalls that classical and quantum Liouvillians are time derivatives. The dissipative fluxes refer to the dynamically accessible microstates. They also provide the basis of the so-called extended thermodynamics [66]. For example, in the linear response theory [67], the dynamical susceptibilities are proportional to the time derivatives of the correlation functions [63]... 

We compute effective thermal transport coefficients for proteins using linear response theory and beginning in the harmonic approximation, with anharmonic contributions included as a correction. The correction can in fact be rather large, as we compute anharmonicity to nearly double the magnitude of the thermal conductivity and thermal diffusivity of myoglobin. We expect that anharmonicity will generally enhance thermal transport in proteins, in contrast, for example, to crystals, where anharmonicity leads to thermal resistance, since most of the harmonic modes of the protein are spatially localized and transport heat only inefficiently. 

One example of the use of linear response theory has been that of Hwang et al. in their studies of an reaction in solution. > o In their work, based on the empirical valence bond (EVB) method discussed earlier, they defined their reaction coordinate Q as the electrostatic contribution to the energy gap between the two valence bond states that are coupled together to create the potential energy surface on which the reaction occurs. Thus, the solvent coordinate is zero at the point where both valence states are solvated equivalently (i.e., at the transition state). Hwang et al. studied the time dependence of this coordinate through both molecular dynamics simulations and through a linear response treatment ... 

Such numerical simulations have played an important role in the development of our understanding of solvation dynamics. For example, they have provided the first indication that simple dielectric continuum models based on Debye and Debey-like dielectric relaxation theories are inadequate on the fast timescales that are experimentally accessible today. It is important to keep in mind that this failure of simple theories is not a failure of linear response theory. Once revised to describe reliably response on short time and length scales, e.g. by using the full k and (O dependent dielectric response function e(k,o , and sufficiently taking into account the solvent structure about the solute, linear response theory accounts for most observations of solvation dynamics in simple polar solvents. 

Electron Drift in a Constant Electric Field. As an example, let us consider the system discussed in the time-of-flight section. In this system, charge carriers are generated close to the injecting contact and drift to the collecting contact under the force of a constant electric field. As discussed above, the current response on a laser pulse has a constant value of Jph = AQIr for 0 < t < t, and drops instantly to zero at t=r. The input signal is a delta function and the output response is a step function. Linear-response theory shows that the system function H s) is the Laplace transform of the impulse response function h(t). In our example ... 

Let us first consider nonequilibrium properties of dense fluids. Linear response theory relates transport coefficients to the decay of position and velocity correlations among the particles in an equilibrium fluid. For example, the shear viscosity ti can be expressed in Green-Kubo formalism as a time integral of a particular correlation function ... 

Screening effects are one of the most important manifestations of the existence of electron-electron interactions in solids. To discuss them, we will first consider a spatially homogeneous system, in which the response at a position r to an electric perturbation localized at ro only depends upon r — ro. This is true, for example, in an homogeneous interacting electron gas. The concept of the dielectric constant refers to the response to a weak perturbation. The relationship between the modification of the charge density Sp(q,(a) and the electrostatic potential F(q,co), is linear in this case, which is the range of validity of the linear response theory. It is then possible to define the electronic susceptibility expressed in... 

In linear response theory the corresponding solvation energies are proportional to the corresponding products q<0>, p and Q where <> denotes the usital observable average. For example, the average potential <0> is proportional in linear response to the perturbation source q. The energy needed to create the charge q is therefore ... 

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