双语化学辞典Chem Lexicon
研究生Graduate 统计热力学 Statistical thermodynamics

平动配分函数Translational partition function

\[q_\text{trans} = \frac{V}{\Lambda^3},\qquad \Lambda = \frac{h}{\sqrt{2\pi m k_\mathrm{B}T}}\]

含义Meaning

Λ 为热德布罗意波长。常温下 \(q_\text{trans}\) 极大(约 \(10^{30}\) 量级每升),意味着平动能级几乎连续,经典处理很好。

Λ is the thermal de Broglie wavelength. At room temperature q_trans is enormous (~10³⁰ per litre), so translational levels are effectively continuous.

符号说明Symbols

符号Symbol含义 Meaning单位 Unit
\(\Lambda\)热波长thermal wavelengthm
\(V\)容器体积volumem³
\(m\)分子质量molecular masskg

推导Derivation

  1. 三维箱中能级 \(\varepsilon = \frac{h^2}{8mL^2}(n_x^2 + n_y^2 + n_z^2)\),三个方向独立:\(q = q_x^3\)。

    Box levels separate in x, y, z: \(q = q_x^3\).

  2. 能级极密,把求和换成积分:\(q_x = \int_0^\infty e^{-n^2h^2/8mL^2k_\mathrm{B}T}dn = \frac{L}{h}\sqrt{2\pi mk_\mathrm{B}T}\)(高斯积分)。

    Replace the sum by a Gaussian integral: \(q_x = (L/h)\sqrt{2\pi mk_\mathrm{B}T}\).

  3. 立方得 \(q = V/\Lambda^3\)。

    Cubing gives \(q = V/\Lambda^3\).

适用条件与局限Assumptions & limitations

  • 要求 \(\Lambda \ll\) 分子间距;否则(极低温、高密度,如液氦、电子气)进入量子简并区。

    Needs Λ ≪ intermolecular spacing; otherwise quantum degeneracy sets in.

例题Worked example

N₂ 在 298 K:Λ = 19 pm;1 L 中 q ≈ 1.4×10³¹。

N₂ at 298 K: Λ = 19 pm; q ≈ 1.4×10³¹ in 1 L.