Content deleted Content added
HappyCamper (talk | contribs) m canonical ensemble instead |
some cleanup |
||
| (28 intermediate revisions by 24 users not shown) | |||
Line 1:
The '''vibrational partition function'''<ref
== Definition ==
For a system (such as a molecule or solid) with uncoupled vibrational modes the vibrational partition function is defined by
<math display="block">Q_\text{vib}(T) = \prod_j{\sum_n{e^{-\frac{E_{j,n}}{k_\text{B} T}}}} </math>
where <math> T </math> is the [[Thermodynamic temperature|absolute temperature]] of the system, <math> k_B </math> is the [[Boltzmann constant]], and <math> E_{j,n} </math> is the energy of the ''j''th mode when it has vibrational quantum number <math> n = 0, 1, 2, \ldots </math>. For an isolated molecule of ''N'' atoms, the number of [[Molecular vibration|vibrational modes]] (i.e. values of ''j'') is {{nowrap|3''N'' − 5}} for linear molecules and {{nowrap|3''N'' − 6}} for non-linear ones.<ref name="Herzberg">G. Herzberg, ''Infrared and Raman Spectra'', Van Nostrand Reinhold, 1945</ref> In crystals, the vibrational normal modes are commonly known as [[phonon]]s.
== Approximations ==
=== Quantum harmonic oscillator ===
The most common approximation to the vibrational partition function uses a model in which the vibrational eigenmodes or [[normal mode]]s of the system are considered to be a set of uncoupled [[quantum harmonic oscillator]]s. It is a first order approximation to the partition function which allows one to calculate the contribution of the vibrational degrees of freedom of molecules towards its thermodynamic variables.<ref name="McQuarrie"/> A quantum harmonic oscillator has an energy spectrum characterized by:
<math display="block">E_{j,n} = \hbar\omega_j\left(n_j + \frac{1}{2}\right)</math>
where ''j'' runs over vibrational modes and <math> n_j </math> is the vibrational quantum number in the ''j''th mode, <math> \hbar </math> is the [[Planck constant]], ''h'', divided by <math> 2 \pi </math> and <math> \omega_j </math>
is the angular frequency of the ''j''th mode. Using this approximation we can derive a closed form expression for the vibrational partition function.
<math display="block">Q_\text{vib}(T) =\prod_j{\sum_n{e^{-\frac{E_{j,n}}{k_\text{B} T}}}}
= \prod_j e^{-\frac{\hbar \omega_j}{2 k_\text{B} T}} \sum_n \left( e^{-\frac{\hbar \omega_j}{k_\text{B} T}} \right)^n
= \prod_j \frac{e^{-\frac{\hbar \omega_j}{2 k_\text{B} T}}}{ 1 - e^{-\frac{\hbar \omega_j}{k_\text{B} T}} }
= e^{- \frac{E_\text{ZP}}{k_\text{B} T}} \prod_j \frac{1}{ 1 - e^{-\frac{\hbar \omega_j}{k_\text{B} T}} }</math>
where <math display="inline"> E_\text{ZP} = \frac{1}{2} \sum_j \hbar \omega_j </math> is total vibrational zero point energy of the system.
Often the [[wavenumber]], <math>\tilde{\nu}</math> with units of cm<sup>−1</sup> is given instead of the angular frequency of a vibrational mode<ref name="Herzberg" /> and also often misnamed frequency. One can convert to angular frequency by using <math> \omega = 2 \pi c \tilde{\nu} </math> where ''c'' is the [[speed of light]] in vacuum. In terms of the vibrational wavenumbers we can write the partition function as
<math display="block">Q_\text{vib}(T) = e^{- \frac{E_\text{ZP}}{k_\text{B} T}} \prod_j \frac{1}{ 1 - e^{-\frac{ h c \tilde{\nu}_j}{k_\text{B} T}} }</math>
It is convenient to define a characteristic vibrational temperature
<math display="block"> \Theta_{i,\text{vib}} = \frac{h \nu_i}{k_\text{B}} </math>
where <math> \nu </math> is experimentally determined for each vibrational mode by taking a spectrum or by calculation. By taking the zero point energy as the reference point to which other energies are measured, the expression for the partition function becomes
<math display="block"> Q_\text{vib}(T) = \prod_{i=1}^f \frac{1}{1-e^{-\Theta_{\text{vib},i}/T}} </math>
== References ==
{{reflist}}
== See also ==
* [[Partition function (mathematics)]]
{{Statistical mechanics topics}}
[[Category:Partition functions]]
| |||