17: Boltzmann Factor and Partition Functions
- Page ID
- 51134
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Statistical Mechanics provides the connection between microscopic motion of individual atoms of matter and macroscopically observable properties such as temperature, pressure, entropy, free energy, heat capacity, chemical potential, viscosity, spectra, reaction rates, etc. Statistical Mechanics provides the microscopic basis for thermodynamics, which, otherwise, is just a phenomenological theory. Microscopic basis allows calculation of a wide variety of properties not dealt with in thermodynamics, such as structural properties, using distribution functions, and dynamical properties – spectra, rate constants, etc., using time correlation functions. Because a statistical mechanical formulation of a problem begins with a detailed microscopic description, microscopic trajectories can, in principle and in practice, be generated providing a window into the microscopic world. This window often provides a means of connecting certain macroscopic properties with particular modes of motion in the complex dance of the individual atoms that compose a system, and this, in turn, allows for interpretation of experimental data and an elucidation of the mechanisms of energy and mass transfer in a system.
- 17.2: The Thermal Boltzman Distribution
- The Boltzmann distribution represents a thermally equilibrated most probable distribution over all energy levels. There is always a higher population in a state of lower energy than in one of higher energy.