We use the equilibrium generalized Langevin equation and its generalized fluctuation-dissipation relation, with the factor in the noise autocorrelation fixing the equilibrium velocity variance. Let be the velocity relaxation function and let a tilde denote a one-sided Laplace transform:The equilibrium velocity autocorrelation function is , soFor completeness, this relation follows without assuming independence of the noise and velocity in a stationary infinite history. The two-sided noise power spectral density is . The stable linear equation has velocity transfer function , soThis is precisely the power spectral density of the even extension of . Stable relaxation removes initial transients with a finite second moment, giving the long-time autocorrelation function defined in the question. All the parameter choices used below have stable relaxation.
Integrating the velocity autocorrelation function twice gives the mean squared displacement from a fixed initial position:A decaying initial transient does not change its asymptotic slope. Therefore the Green-Kubo formula for diffusion givesFor the given friction memory kernel, direct integration yieldsAt , the integrated friction is , henceThe relaxation denominator here is . Its roots have negative real parts by the cubic Routh-Hurwitz criterion, since all coefficients are positive and . This justifies the decay and integrability used above. The diffusion coefficient depends on the area under the friction memory kernel, not just its value at zero.
For , , , the friction memory kernel and its Laplace transform areUsing the generalized fluctuation-dissipation relation with equilibrium velocity variance , the velocity autocorrelation function has Laplace transformAll three poles are negative, so the stationary relaxation is stable. A partial fraction decomposition givesTaking the inverse Laplace transform givesThe negative middle coefficient is compatible with an autocorrelation function; individual terms in a partial fraction decomposition need not themselves be separate physical modes with positive weights. Several useful checks follow directly:The Volterra integral equation for predicts exactly and . Its integral is also , agreeing with the Green-Kubo formula for diffusion.
The integrated friction is exactlyFor every finite , the roots of have negative real parts. The Green-Kubo formula for diffusion therefore gives the diffusion coefficient directly:ConsequentlyIntegrating the limiting velocity autocorrelation function gives the same value, . Computing before taking the limit also avoids having to justify an interchange of the infinite-time integral and the parameter limit.
Velocity autocorrelation function 2026-10-25
The unnormalized autocorrelation function of a stationary velocity. For zero mean, is the velocity variance. It is different from the normalized autocorrelation function often used in time series.
If , integrating the two-time covariance over the square givesThis identity connects a mean squared displacement to the Green-Kubo formula for diffusion.