Computed Spin-Spin Coupling Constants (~1J_(X-Y)) in Molecules H_mX-YH_n for X and Y = ~(13)C, ~(15)N, and ~(31)P: Comparisons with Experiment and Insights into the Signs of ~1J_(X-Y)

Janet E. Del Bene; Jose Elguero; Ibon Alkorta

首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Computed Spin-Spin Coupling Constants (~1J_(X-Y)) in Molecules H_mX-YH_n for X and Y = ~(13)C, ~(15)N, and ~(31)P: Comparisons with Experiment and Insights into the Signs of ~1J_(X-Y)

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Computed Spin-Spin Coupling Constants (~1J_(X-Y)) in Molecules H_mX-YH_n for X and Y = ~(13)C, ~(15)N, and ~(31)P: Comparisons with Experiment and Insights into the Signs of ~1J_(X-Y)

机译：X和Y的分子H_mX-YH_n中的计算自旋-自旋耦合常数（〜1J_（XY））=〜（13）C，〜（15）N和〜（31）P：与实验的比较以及对符号的认识〜1J_（XY）

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One-bond X-Y spin-spin coupling constants (~1J_(X-Y)) for 18 H_mX-YH_n molecules, with X and Y = ~(13)C, ~(15)N, and ~(31)P, have been computed using the equation-of-motion coupled-cluster singles and doubles method. The molecules investigated include all possible combinations of these three elements bonded with single, double, and triple bonds. The computed coupling constants are in good agreement with experiment over a range that extends from -250 to +200 Hz. With only two exceptions, the sign of the Fermi-contact (FC) term is the same as the sign of ~1J_(X-Y), but the FC term may or may not be a good quantitative estimate of ~1J_(X-Y). When reduced spin-spin coupling constants (~1K_(X-Y)) are used for comparing coupling constants involving different atoms, a linear relationship is observed between ~1K_(X-N) and ~1K_(X-P). The signs of ~1J_(X-Y) for approximately half of the molecules included in this study are exceptions to the Dirac vector model. The recently proposed NMR triplet wave function model has been used to provide insight into the variation of the signs of these one-bond spin-spin coupling constants.

机译：计算了18个H_mX-YH_n分子的X键和Y =〜（13）C，〜（15）N和〜（31）P的单键XY自旋耦合常数（〜1J_（XY））使用运动方程组耦合单打和双打方法。研究的分子包括这三个以单键，双键和三键结合的元素的所有可能组合。计算的耦合常数在从-250到+200 Hz的范围内与实验非常吻合。除两个例外外，费米接触（FC）项的符号与〜1J_（X-Y）的符号相同，但FC项可能是或不一定是〜1J_（X-Y）的良好定量估计。当使用降低的自旋-自旋耦合常数（〜1K_（X-Y））比较涉及不同原子的耦合常数时，在〜1K_（X-N）和〜1K_（X-P）之间观察到线性关系。这项研究中包括的大约一半分子的〜1J_（X-Y）的符号是Dirac矢量模型的例外。最近提出的NMR三重态波函数模型已用于洞察这些单键自旋-自旋耦合常数的符号变化。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2004年第16期|共6页
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Janet E. Del Bene; Jose Elguero; Ibon Alkorta;
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1. Computed Spin-Spin Coupling Constants (~1J_(X-Y)) in Molecules H_mX-YH_n for X and Y = ~(13)C, ~(15)N, and ~(31)P: Comparisons with Experiment and Insights into the Signs of ~1J_(X-Y) [J] . Janet E. Del Bene, Jose Elguero, Ibon Alkorta The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2004,第16期

机译：X和Y的分子H_mX-YH_n中的计算自旋-自旋耦合常数（〜1J_（XY））=〜（13）C，〜（15）N和〜（31）P：与实验的比较以及对符号的认识〜1J_（XY）
2. Variation of one-bond X-Y coupling constants (1)J(X-Y) and the components of (1)J(X-Y) with rotation about the X-Y bond for molecules HmX-YHn, with X, Y=N-15, O-17, P-31, S-33: The importance of nonbonding pairs of electrons [J] . Del Bene JE, Elguero J The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2007,第13期

机译：具有X，Y = N-15，O-17的分子HmX-YHn的单键XY耦合常数（1）J（XY）和（1）J（XY）的分量随绕XY键旋转的变化，P-31，S-33：非键电子对的重要性
3. Predicted signs of reduced two-bond spin-spin coupling constants (K-2h(X-Y)) across X-H-Y hydrogen bonds [J] . Del Bene JE, Elguero J Magnetic Resonance in Chemistry: MRC . 2004,第5期

机译：跨X-H-Y氢键的双键自旋-自旋偶合常数（K-2h（X-Y））降低的预测迹象
4. Variation of one-bond X-Y coupling constants1J(X-Y) and the components of1J(X-Y) with rotation about the X-Y bond for molecules HmX-YHn, with X, y =15N, 17O, 31P, 33S; the importance of nonbonding pairs of electrons [O] . Del Bene Janet E., Elguero José 2013

机译：对于分子HmX-YHn，X，y = 15N，17O，31P，33S，一键X-Y耦合常数1J（X-Y）和1J（X-Y）的分量围绕X-Y键旋转而变化；非键电子对的重要性

Computed Spin-Spin Coupling Constants (~1J_(X-Y)) in Molecules H_mX-YH_n for X and Y = ~(13)C, ~(15)N, and ~(31)P: Comparisons with Experiment and Insights into the Signs of ~1J_(X-Y)

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