Calculations exploring the nature and extent of the inductive effect in organic chemistry

The inductive effect is a foundational concept in chemistry relating to the way charge is transmitted within a molecule as a result of substituents. We find that the description of the inductive effect in textbooks is sometimes incorrect and a more refined version is necessary. The data herein demonstrates this.The dataset is organised in the following way:Calculations on 1-substituted pentanes. These show that the effect of substituents (halogens, etc.) are not transmitted along the carbon chain in the way commonly described in textbooks. Various methods of charge analysis have been used, and all lead to the same conclusions.Calculations on a small number of aromatic compounds confirm this to be the case here as well.For carboxylic acids, the calculations show that we should only consider the charge redistribution in the carboxylate anion, and these data do not follow the expected electronegativity trends. In particular, the effects are greater for Cl than for F, which shows that polarizability is more important than electronegativity.The field effect is an importance concept in structural/physical organic chemistry. The dataset contains a number of examples in which the field effect can be presented as a through-orbital polarization effect (which is inherently directional) rather than the commonly stated through-space effect. On this basis, the field effect should not be considered to be a distinct effect.To support the calculations on polarizability, a series of calculations on 1-fluoropentane is included, with a computationally applied charge. These data confirm that the effect is not transmitted through the bonds in a decreasing sense (as is commonly taught) but can again best be represented as a broader polarization of molecular orbitals.

诱导效应（inductive effect）是化学中的一个基础概念，用于描述分子内因取代基引发的电荷传递方式。我们发现，教科书中对诱导效应的阐释有时存在疏漏，亟需更为精炼的修正版本，本数据集即可对此进行佐证。
本数据集的组织形式如下：
对1-取代戊烷的计算分析。结果表明，取代基（如卤素等）并未按照教科书中通常描述的方式沿碳链传递其效应。本研究采用了多种电荷分析方法，所有方法均得到了一致的结论。
对少量芳香族化合物的计算验证同样证实了上述结论。
针对羧酸类物质，计算结果表明，仅需考虑羧酸根阴离子（carboxylate anion）内的电荷重分布过程，且相关数据并不符合预期的电负性（electronegativity）变化趋势。尤为关键的是，氯（Cl）的效应强于氟（F），这证明极化率（polarizability）相较于电负性更为重要。
场效应（field effect）是结构/物理有机化学中的重要概念。本数据集包含多个示例，表明场效应可被归类为一种经由轨道的极化效应（其本身具有固有方向性），而非通常所宣称的经由空间的传递效应。基于此，场效应不应被视为一种独立的效应。
为支撑与极化率相关的计算结论，数据集纳入了针对1-氟戊烷的系列计算，并通过计算手段施加了人工电荷。这些数据进一步证实，该效应并非如常规教学中所阐述的那样沿化学键逐级衰减传递，反而更适合用更为宽泛的分子轨道（molecular orbitals）极化来进行描述。