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间接核旋转-旋转合张力器的周期趋势:对于介质二氧化的相对论密度函数计算
David L Bryce1, Roderick E Wasylishen, Jochen Autschbach
1Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada.
Journal of the American Chemical Society
|April 25, 2002
概括
使用ZORA-DFT的相对论计算准确地预测了二原子素中的核自旋-自旋合 (J) 张量. 这些J张量显示了原子数的线性趋势,突出显示了重原子自旋轨道效应的重要性.
科学领域:
- 量子化学 是一个量子化学.
- 计算光谱学是一种计算光谱学.
- 分子中的相对论效应.
背景情况:
- 间接核旋转合 (J) 张量对分子结构和动力学至关重要.
- 非相对论方法往往无法解释J张量,特别是对于重元素.
- 对于含有重原子的分子,相对论效应变得显著.
研究的目的:
- 应用相对论零阶正则近似密度函数理论 (ZORA-DFT) 来计算J张量.
- 为了研究二原子素分子 (F2到At2,以及异质核对) 中的J张量.
- 了解重原子系统中相对论效应和合机制的作用.
主要方法:
- 使用相对论ZORA-DFT实现计算J张量.
- 将该方法应用于一系列同核和异核二原子素.
- 将ZORA-DFT结果与多配置自一致场 (MCSCF) 计算和实验数据进行比较.
主要成果:
- ZORA-DFT准确地复制了F2和ClF的J张量,与MCSCF结果相匹配.
- 降低的同位素 (Kiso) 和异位素 (DeltaK) 合常数显示大多数素对原子数的乘积有线依赖.
- 偏磁旋转轨道合是基索的主要贡献者 (~70-80%) .
结论:
- ZORA-DFT是计算J张量的一种可靠方法,特别适用于重原子系统.
- 相对论旋转轨道校正对于涉及重核的精确J张量计算至关重要.
- 这项研究揭示了两原子素之间J合常数的周期性趋势.
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