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

自旋–自旋裂分(n + 1 规律)Spin–spin splitting (n + 1 rule)

\[M = 2nI + 1 \xrightarrow{I = 1/2} n + 1,\qquad \text{强度比} = \binom{n}{k},\ k = 0, \ldots, n\]\[M = 2nI + 1 \xrightarrow{I = 1/2} n + 1,\qquad \text{intensity ratio} = \binom{n}{k},\ k = 0, \ldots, n\]

含义Meaning

一级谱中,与 n 个等价核偶合的信号裂分为 2nI + 1 重峰;对 ¹H(I = 1/2)即 n + 1 重峰,强度比为帕斯卡三角系数,峰间距等于偶合常数 J。

In first-order spectra, coupling to n equivalent nuclei splits a signal into 2nI + 1 lines; for ¹H (I = ½) that is n + 1 lines with binomial intensities spaced by J.

符号说明Symbols

符号Symbol含义 Meaning单位 Unit
\(n\)等价邻近核数number of equivalent coupled nuclei1
\(I\)邻近核的自旋量子数spin of the coupled nucleus1
\(J\)偶合常数coupling constantHz

推导Derivation

  1. 每个邻近 ¹H 的自旋 α 或 β 使观测核的局部场略增或略减,信号一分为二(间距 J)。

    Each neighbouring proton, α or β, nudges the local field up or down, splitting the line by J.

  2. n 个等价邻核的总 \(m\) 取值 \(-n/2, \ldots, n/2\),共 n + 1 种;每种组合数为 \(\binom{n}{k}\)。

    n equivalent neighbours give n + 1 total m values with multiplicities \(\binom{n}{k}\).

  3. 与两组不等价核偶合(\(J_1 \ne J_2\)):峰数为 \((n_1+1)(n_2+1)\),如 dd、dt。

    Two inequivalent sets give \((n_1+1)(n_2+1)\) lines (dd, dt, …).

  4. 与氘(I = 1)偶合:2n + 1,如 CHD₂ 为 1:2:3:2:1 五重峰(DMSO-d₆ 残留峰)。

    With deuterium (I = 1): 2n + 1, e.g. 1:2:3:2:1 for CHD₂.

适用条件与局限Assumptions & limitations

  • 只在 Δν ≫ J(约 > 10 倍)时成立;否则出现屋顶效应、AB、ABX 等二级谱。

    Valid only for Δν ≫ J; otherwise roofing and AB/ABX patterns.

  • 化学等价但磁不等价的核(如对二取代苯 AA′BB′)不服从简单规律。

    Chemically but not magnetically equivalent nuclei (AA′BB′) do not follow the rule.