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  • Boltzmann Proof

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    Tanmoy Roy
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    Boltzmann Proof

    Загружено:

    Tanmoy Roy

    Авторское право:

    Attribution Non-Commercial (BY-NC)
    Скачайте в формате PDF или читайте онлайн в Scribd
    Отметить как неприемлемый контент
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    | Home Page | Topics | Evaluation | Assignments | Resources | News | Statistical Mechanics Introduction Statistical mechanies provides a bridge between the macroscopic realm of classical thermodynamics and the microscopic realm of atoms and molecules. We are able to use computational methods to calculate the thermodynamic parameters of a system by applying statistical mechanics. Of particular interest in biochemistry is the ability to calculate free energies associated with a variety of processes such as ligand-receptor interaction and protein stabilty. This review of some basic principles of statistical mechanics serves as a prelude to discussions of fiee energy simulations. ‘We must remember that the energies of molecules, atoms, or electrons are quantized. To describe chemical systems we must know the energies of the quantum states and the distribution of particles (ie., molecules, atoms, or electrons) among the quantum states. The Schrodinger equation that we discussed in the section on ‘quantum mechanics provides a method for calculating the allowed energies. The Boltamam distribution law that is a fundamental principle in statistical mechanics enables us to determine how a large number of particles distribute themselves throughout a set of allowed energy levels. Presented below are two derivations of the Boltzmann distribution law, one based on a treatment by Nash [1], and the second, by Barrow [2]. Both approaches are given as a means to ilistrate that multiple ways are sometimes available to develop a concept Boltzmann Distribution Law (adapted from Nash) Microstates and Configurations Consider a simple assembly of three localized (ie., distinguishable) particles that share three identical quanta of energy. These quanta can be distributed among the particles in ten possible distributions as ilustrated in the — Each of the ten distributions is called a microstate; in our example the ten microstates fll into three groups, or configurations, denoted A, B, and C, When dealing with only three particles, we can count the number of microstates and configurations, but for larger numbers of particles, we need to calculate them. Our simple example above can be used to understand how to calculate the number of microstates and configurations. For configuration B: The two-quanta parcel of energy can be assigned to any ofthe three particles, the one-quantum parcel to either of the two remaining particles, and the zero-quantum parcel to the remaining particle, Thus, the total number of ways in which assignments can be made is 3-2-1=31=6 For configuration A: We again have three choices in assigning the first (three-quanta) parcel of energy, two choices when we assign the second (zero-quantum), and one choice when we assign the third (zero- quantum). But because the last two parcels are the same, the final distribution is independent of the order in which they are distinguishable assignments collapse into one microstate because the two particles end up in the same quantum level. Thus, the total number of microstates associated with configuration A is For configuration C: We have triple occupancy of the first quantum level and the final distribution is independent of the order in which the particles are assigned. Thus, we have one microstate. Bily This approach can be generalized to a larger number (N) of localized particles. We have N choices of the particle to which we assign the first parcel of energy, (N=1) choices in assigning the second, etc, to give a w (n)(N-1)(N-2)---(@)=™! distinguishable possibilities ifno two energy parcels are the same. Ifsome number (mg) ofthe parcels are the same, we can have only N/n,/ distinct microstates. Symbolizing by IV the total number of microstates in a given configuration, we can write For very large NY, itis necessary to deal with natural logarithms. That is, In W=In Mt -lh ((x

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