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Getfert, Sebastian: Escape processes far from thermal equilibrium : path integrals and force spectroscopy. 2009
Inhalt
List of Symbols
List of Figures
General introduction and concepts
Introduction
Basic concepts of stochastic modeling and rate theory
The Langevin equation with Gaussian white noise
Equation of motion for a general reaction coordinate
Fokker-Planck equation
Escape from a static potential
Kramers rate
Single-molecule force spectroscopy: Theory and evaluation of experimental data
Principle and theory of single-molecule force spectroscopy
Introduction
Single-molecule force spectroscopy with the AFM
Atomic force microscope
Force spectroscopy
Force distance curves
Force spectroscopy with other techniques
Theoretical modeling of bond rupture
Bond rupture as thermally activated decay of a metastable state
Distribution of rupture forces
Rate Ansatz
Evaluation of single-molecule force spectroscopy experiments
Parameter estimation: Properties of the maximum likelihood estimator
Maximum likelihood estimator
Asymptotic properties
Cramér-Rao bound
Parameter inference: Main steps for the practical application
Application to Bell's model
Statistical uncertainties of Bell's model
Illustration for computer generated data
Extension of Bell's model
Discussion
Incompatibilities between experiment and theory
Revealing incompatibilities between experiment and theory
Heterogeneous bond model
Influence of the parametric Ansatz for the rate distribution
Other distributions of
Variation of
Preprocessing the data: Experimental hints for a heterogeneity of bonds
Effects of non-equilibrium initial distributions
Concluding discussion
Escape rates of overdamped Brownian particles far from thermal equilibrium
A unified approach to the approximation of escape rates
Introduction
General formulation of the problem
Model
Definition of the instantaneous escape rate
Time transformation
Theoretical framework
Notation
Path integrals for the transition probability density
Optimizing paths and limitations
A new path integral approach to the escape problem
Renewal approach
Approximation of the first passage time density
Behavior of the optimizing paths in vicinity of the stable and unstable orbit
Asymptotics of the integrand
Expansion around asymptotic paths
Main steps for a practical application
Adiabatically slowly modulated potentials
Examples
Piecewise parabolic potential: General case with time-dependent coefficients
The piecewise parabolic potential: Periodic tilting
The piecewise parabolic potential: Moderately fast driving
The cubic potential
Time-dependent temperatures
Suppression of thermally activated escape by heating
Model
Dynamics
Case 1: Equilibrium condition
Case 2: Effective escape rate
Temperature modulations
Model potential
Transition rate
The quasi-stationary distribution
Non-equilibrium stabilization by heating
Discussion
Summary and outlook
Single-molecule force spectroscopy
Escape rates far from thermal equilibrium
Appendices
Supplements to chapter 4
Asymptotic distribution of the maximum likelihood estimate
Statistical uncertainties for Bell's model
Optimal bin-width for histograms
Supplements to chapter 6
Limit of the integral (6.71)
Series expansion of the first passage time density for a piecewise linear potential
Escape rate for an adiabatically slowly driven, piecewise parabolic potential
Escape rate from a piecewise parabolic potential: Rectangular pulse
Bibliography
Acknowledgments