双语化学辞典Chem Lexicon
本科Undergraduate 分子光谱与结构测定 Molecular spectroscopy & structure determination

拉莫尔频率与核磁共振条件Larmor frequency and the NMR resonance condition

\[\nu_0 = \frac{\gamma B_0}{2\pi},\qquad \Delta E = \gamma\hbar B_0,\qquad \frac{N_\beta}{N_\alpha} = e^{-\gamma\hbar B_0/k_\mathrm{B}T}\]

含义Meaning

自旋 1/2 的核在磁场 B₀ 中分裂为两个能级,吸收频率等于核磁矩进动的拉莫尔频率。能差极小,上下能级布居差只有约 10⁻⁵,所以 NMR 灵敏度低,需要强磁场。

A spin-½ nucleus in field B₀ has two levels; it absorbs at the Larmor precession frequency. The gap is tiny, so the population difference is ~10⁻⁵ — hence NMR’s low sensitivity and need for strong magnets.

符号说明Symbols

符号Symbol含义 Meaning单位 Unit
\(\gamma\)旋磁比(¹H 2.675×10⁸ rad·s⁻¹·T⁻¹)gyromagnetic ratio (¹H 2.675×10⁸)rad·s⁻¹·T⁻¹
\(B_0\)外磁场applied fieldT
\(\nu_0\)共振频率resonance frequencyHz

推导Derivation

  1. 核磁矩 \(\boldsymbol\mu = \gamma\hat{\mathbf I}\),在磁场中能量 \(E = -\mu_zB_0 = -\gamma\hbar m_IB_0\),\(m_I = \pm\tfrac12\)。

    Nuclear moment \(\mu = \gamma I\); energy \(E = -\gamma\hbar m_IB_0\).

  2. 两能级差 \(\Delta E = \gamma\hbar B_0 = h\nu_0\),得 \(\nu_0 = \gamma B_0/2\pi\)。

    \(\Delta E = \gamma\hbar B_0 = h\nu_0\).

  3. 经典图像:磁矩受力矩绕 B₀ 进动,角频率 \(\omega_0 = \gamma B_0\)。

    Classically the moment precesses at \(\omega_0 = \gamma B_0\).

  4. 布居差 \(\approx \gamma\hbar B_0/(2k_\mathrm{B}T)\):¹H 在 9.4 T、298 K 约 3×10⁻⁵。

    Population excess ≈ 3×10⁻⁵ for ¹H at 9.4 T and 298 K.

适用条件与局限Assumptions & limitations

  • 化学环境使局部磁场 \(B_\text{loc} = B_0(1 - \sigma)\),频率随之偏移(化学位移)。

    Shielding makes \(B_\text{loc} = B_0(1-\sigma)\), shifting the frequency (chemical shift).

  • I > 1/2 的核有电四极矩,谱线常因快速弛豫而变宽。

    Quadrupolar nuclei (I > ½) often give broad lines.

例题Worked example

¹H 在 9.4 T:ν₀ = 2.675×10⁸×9.4/2π = 400 MHz(“400 MHz 核磁”);¹³C 约 100 MHz。

¹H at 9.4 T resonates at 400 MHz; ¹³C at ~100 MHz.