Hara Takeshi, Hasebe Masatoshi, Tsuneda Takao, Naito Toshio, Nakamura Yuiga, Katayama Naoyuki, Taketsugu Tetsuya, Sawa Hiroshi
Department of Applied Physics, Nagoya University, Nagoya 464-8603, Japan.
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-8628, Japan.
J Am Chem Soc. 2024 Aug 28;146(34):23825-23830. doi: 10.1021/jacs.4c05673. Epub 2024 Jul 17.
Recent advent of diverse chemical entities necessitates a re-evaluation of chemical bond concepts, underscoring the importance of experimental evidence. Our prior study introduced a general methodology, termed Core Differential Fourier Synthesis (CDFS), for mapping the distribution of valence electron density (VED) in crystalline substances within real space. In this study, we directly compare the VED distributions obtained through CDFS with those derived from high-accuracy theoretical calculation using long-range corrected density functional theory, which quantitatively reproduces accurate orbital energies. This comparison serves to demonstrate the precision of the CDFS in replicating complex details. The VED patterns observed experimentally exhibited detailed structures and phases of wave functions indicative of sp hybrid orbitals, closely aligning with theoretical predictions. This alignment underscores the utility of our approach in gathering quantum chemical data experimentally, a crucial step for discussing the chemical properties, such as reaction mechanisms.
近年来，各种化学实体的出现使得有必要重新评估化学键概念，这突出了实验证据的重要性。我们之前的研究引入了一种通用方法，称为核心差分傅里叶合成（CDFS），用于在实空间中绘制晶体物质中价电子密度（VED）的分布。在本研究中，我们将通过CDFS获得的VED分布与使用长程校正密度泛函理论进行的高精度理论计算得出的分布直接进行比较，该理论能定量再现精确的轨道能量。这种比较旨在证明CDFS在复制复杂细节方面的精度。实验观察到的VED模式展现出了表明sp杂化轨道的波函数的详细结构和相位，与理论预测密切吻合。这种吻合突出了我们的方法在通过实验收集量子化学数据方面的实用性，这是讨论化学反应机理等化学性质的关键一步。
