尺寸很重要:对高贵气体三氧化物冠冕的计算洞察
Soumya Ranjan Dash1,2, Himanshu Sharma1,2, Mrityunjay K Tiwari3
1Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Pune 411008, India.
Inorganic chemistry
|February 19, 2024
概括
量子化学计算表明,皇冠乙烯可以稳定爆炸性贵气三氧化物,如XeO3. 较大的皇冠乙烯和C-H··O相互作用增强了稳定性,观察到9的创纪录的异协调数.
科学领域:
- 计算化学是一种计算化学.
- 无机化学 无机化学 无机化学
- 材料科学是一种材料科学.
背景情况:
- 三氧化物 (XeO3) 是一种高度易爆和易冲击的化合物.
- 稳定反应性贵重气体化合物对于安全处理和潜在应用至关重要.
研究的目的:
- 研究 XeO3 和其他贵重气体三氧化物 (KrO3,ArO3) 与富含电子的皇冠和它们的类类似物复合的过程.
- 探索提高爆炸性贵重气体化合物的稳定性的方法.
主要方法:
- 使用了量子化学计算.
- 计算了基数组叠加错误 (BSSE) 纠正的相互作用能量.
- 分析包括静电电位 (ESP) 映射,维伯格键索引 (WBI),贝德原子在分子理论 (AIM),自然键轨道 (NBO) 分析,非共价相互作用 (NCI) 图形和能量分解分析 (EDA).
主要成果:
- 在贵重气体三氧化物和皇冠之间形成的附加物表现出强烈的非共价相互作用,相互作用能量在-13.0到-48.2kcal/mol之间.
- 复合稳定性随着更大的皇冠乙烯环大小而增加,并从 XeO3 降低到 ArO3.3.
- 鉴定出C-H···O和分散相互作用是较大的皇冠乙烯的关键稳定因素.
- 在XeO3复合物中与18-crown-6的thio模拟物观察到的异协调数为9,超过了之前报告的值.
结论:
- 皇冠和它们的类类似物可以通过显著的非对应相互作用有效地稳定贵重气体三氧化物.
- 该研究强调了定制的超分子结构在管理危险化合物的潜力.
- 对于的前所未有的协调号码表明了贵重气体化学中的新可能性.
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