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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Role of H-Optimization in the Computed Intermolecular Interactions and Charge-Transfer Integrals in Diketopyrrolopyrroles
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Role of H-Optimization in the Computed Intermolecular Interactions and Charge-Transfer Integrals in Diketopyrrolopyrroles

机译：H-Optimization在Diketopyrolopyroles中计算的分子间相互作用和电荷转移积分的作用

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Small organic conjugated systems displaying one-dimensional stacking motifs in the solid state that facilitate charge propagation are highly desirable. Noncovalent interactions, although weak, can synergistically provide those supra-molecular architectures with large binding energies and associated thermal integrity. Amongst the plethora of intermolecular interactions contributing toward the overall lattice energy and stability of the charge-propagation supramolecular architectures, H-bonding interactions are well-known to play a pivotal role. Despite their critical contribution, the positions of hydrogen atoms in X-ray crystallographic data are parameterized, which can lead to significant changes in the computed intermolecular interactions. Herein, we report for the first time an analysis of the role that the optimization of the H atoms in X-ray structures has in the computed intermolecular interactions energies in diketopyrrolopyrroles (DPPs). A large dataset comprising 94 dimer pairs from 19 different DPP-based systems, including three pigment analogues, was employed. In total, more than 1400 H-X chemical bonds were considered and optimized using the M06-2X density functional at the 6-311G(d) level. Intermolecular interactions were computed for the H-optimized geometries and compared to those from nonoptimized counterparts. We report that in 35 out of the 94 dimer pairs investigated (37%), the computed intermolecular interactions were at least 2.5 kJ mol(-1) larger on progression to the Hoptimized geometries. In turn, lower computed values were yielded upon H-optimization computed for 8 out of the 94 dimer pairs (8%), with one case exhibiting a difference greater than 2.5 kJ mol(-1). In line with the negligible changes to electron density and wavefunction overlap, the computed changes on the transfer integrals for the hole and electron were always lower than 1 kJ mol(-1). The observed changes to computed intermolecular interactions can play a critical role in det
机译：在促进电荷传播的固态中显示一维堆叠图案的小有机共轭系统是非常理想的。虽然弱，但虽然弱，但能够协同提供具有大的结合能和相关热完整性的那些超分子架构。在往整体晶格能量和电荷繁殖超分子架构的整体晶格能量和稳定性的血流分子相互作用中，众所周知，H键合相互作用是发挥枢转作用。尽管存在关键贡献，但是参数化X射线晶体数据中的氢原子的位置，这可能导致计算的分子间相互作用的显着变化。在此，我们首次报告了对X射线结构中H原子优化的作用的分析在Diketopyrolopyroles（DPP）中的计算分子间相互作用能量中。使用包括来自19个不同DPP的基于DPP的系统的大型数据集，包括三种颜料类似物。总共有超过1400 H-X化学键，并在6-311g（d）水平下使用M06-2X密度官能进行优化。针对H优化几何形状计算的分子间相互作用，并与非优化对应物的相比。我们认为，在进行的94二聚体对中的35中（37％），计算的分子间相互作用至少为2.5kJ摩尔（-1），而是较大的进展到氧化的几何形状。反过来，在94二聚体对（8％）中计算的H次优化时，产生较低的计算值，其中一个情况表现出大于2.5kJ摩尔（-1）的差异。符合电子密度和波消效重叠的可忽略的变化，孔和电子的转移积分的计算变化总是低于1kJ摩尔（-1）。观察到的经过计算的分子间相互作用的变化可以在Det中发挥重要作用

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