Puzzarini Cristina, Cazzoli Gabriele, Harding Michael E, Vázquez Juana, Gauss Jürgen
Dipartimento di Chimica "Giacomo Ciamician," Università degli Studi di Bologna, Via Selmi 2, I-40126 Bologna, Italy.
Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Postfach 3640, D-76021 Karlsruhe, Germany.
J Chem Phys. 2015 Mar 28;142(12):124308. doi: 10.1063/1.4916068.
Guided by theoretical predictions, the hyperfine structures of the rotational spectra of mono- and bideuterated-water containing (17)O have been experimentally investigated. To reach sub-Doppler resolution, required to resolve the hyperfine structure due to deuterium quadrupole coupling as well as to spin-rotation (SR) and dipolar spin-spin couplings, the Lamb-dip technique has been employed. The experimental investigation and in particular, the spectral analysis have been supported by high-level quantum-chemical computations employing coupled-cluster techniques and, for the first time, a complete experimental determination of the hyperfine parameters involved was possible. The experimentally determined (17)O spin-rotation constants of D2 (17)O and HD(17)O were used to derive the paramagnetic part of the corresponding nuclear magnetic shielding constants. Together with the computed diamagnetic contributions as well as the vibrational and temperature corrections, the latter constants have been employed to confirm the oxygen nuclear magnetic shielding scale, recently established on the basis of spin-rotation data for H2 (17)O [Puzzarini et al., J. Chem. Phys. 131, 234304 (2009)].
在理论预测的指导下，对含(^{17}O)的单氘代水和双氘代水转动光谱的超精细结构进行了实验研究。为了达到分辨由氘四极耦合以及自旋 - 转动（SR）和偶极自旋 - 自旋耦合引起的超精细结构所需的亚多普勒分辨率，采用了兰姆凹陷技术。实验研究，特别是光谱分析，得到了采用耦合簇技术的高水平量子化学计算的支持，并且首次能够对所涉及的超精细参数进行完整的实验测定。通过实验测定的(D_2^{17}O)和(HD^{17}O)的(^{17}O)自旋 - 转动常数，推导出相应核磁屏蔽常数的顺磁部分。连同计算出的抗磁贡献以及振动和温度校正，这些常数被用于确认最近基于(H_2^{17}O)的自旋 - 转动数据建立的氧核磁屏蔽标度[Puzzarini等人，《化学物理杂志》131，234304（2009）]。
