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首页> 外文期刊>Journal of theoretical & computational chemistry >Theoretical investigation of substitution effect on the proton transfer mechanism in 3-mercapto-propenethial
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Theoretical investigation of substitution effect on the proton transfer mechanism in 3-mercapto-propenethial

机译：对3-巯基丙烯中质子传递机理的取代作用的理论研究

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摘要

We present detailed theoretical studies of the proton transfer (PT) in the 3-Mercapto-propenethial (MP) and in some of its derivatives. The effect of substitution on the transition state structures corresponding to the PT in R2 or R1(3) positions is studied by using B3LYP/6-311++G** level of theory in gas phase and water solution. The following substituents have been taken into consideration: Cl, F, OH, SH, OCH_3, SCH_3, CHO, NO_2, CCH and OCF_3. For the different derivatives of 3-MP, we have computed geometries and potential energy curves for the intramolecular PT in their ground. Also, the excited-state properties of intramolecular hydrogen bonding in substituted systems have been investigated theoretically using the time-dependent density functional theory method. The π-electron delocalization parameter (Q) and HOMA index as a geometrical indicator of a local aromaticity are investigated. Natural bond orbital (NBO) analysis was also performed for better understanding the nature of intramolecular interactions. The results of analysis by Quantum theory of ?Atoms in Molecules? and NBO method fairly support the DFT results. Correlations between the PT reaction barrier versus topological parameters, ν(S-H) and γ(S-H) are also probed. The obtained results showed a strong influence of the R substituent on the PT reaction barrier changes. Numerous correlations between topological, geometrical, thermodynamic properties and energetic parameters were also found.
机译：我们介绍了3-巯基-丙烯（MP）及其某些衍生物中质子转移（PT）的详细理论研究。通过在气相和水溶液中使用B3LYP / 6-311 ++ G **理论水平研究取代对R2或R1（3）位置PT对应的过渡态结构的影响。已考虑以下取代基：Cl，F，OH，SH，OCH_3，SCH_3，CHO，NO_2，CCH和OCF_3。对于3-MP的不同导数，我们已经计算了其内分子内PT的几何形状和势能曲线。同样，已经使用时间依赖性密度泛函理论方法对取代体系中分子内氢键的激发态性质进行了理论研究。研究了π电子离域参数（Q）和HOMA指数作为局部芳香性的几何指标。还进行了自然键轨道（NBO）分析，以更好地了解分子内相互作用的性质。量子理论对“原子原子”的分析结果。 NBO方法相当支持DFT结果。还探究了PT反应势垒与拓扑参数ν（S-H）和γ（S-H）之间的相关性。所得结果表明R取代基对PT反应势垒变化的强烈影响。还发现了拓扑，几何，热力学性质和能量参数之间的许多相关性。

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