Cationic Noble Gas Hydrides: A Theoretical Investigation of Dinuclear HNgFNgH+ (Ng = He-Xe)
Cationic Noble Gas Hydrides: A Theoretical Investigation of Dinuclear HNgFNgH+ (Ng = He-Xe)
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DOI：
10.1021/jp102018n
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发表时间：
2010-07-15
影响因子：
2.9
通讯作者：
Grandinetti, Felice
中科院分区：
文献类型：
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作者：
Borocci, Stefano;Bronzolino, Nicoletta;Grandinetti, Felice
在B3LYP、MP2和CCSD(T)理论水平上的理论计算揭示了含有两个Ng原子的阳离子稀有气体氢化物的可能存在。这些种类具有HNgFNgH(+) （Ng = He-Xe）的通式，是中性HNgF的阳离子对应物。优化后的几何形状、谐波频率和键合性质指向氟离子阴离子和两个共价H-Ng（+）阳离子之间的离子偶极配合物，最佳表述为（H-Ng(+)）(2)F-。HXeFXeH+与最近实验观测到的HXeOXeH也是等电子的（Khriachtchev et al.）。j。化学。社会科学学报，2008,30(6):6114-6118。所得HNgFNgH（+）在解离成HNg(+) + HNgF和HNg(+) + H + Ng + F时热化学稳定，但在HNg（+）的损失（形成HNg(+) + Ng）和H2F+（形成两个Ng原子）方面基本不稳定。这些分解通过弯曲跃迁结构进行，只有最重的HAtFArH+、HKrFKrH+和HXeFXeH+受到足够大的能垒（约10-15千卡摩尔（-1））的保护，以支持其可能的亚稳态。与其他系列稀有气体化合物一样，氖阳离子HNeFNeH+是各种HNgFNgH（+）中最不稳定的。
Theoretical calculations at the B3LYP, MP2, and CCSD(T) levels of theory disclose the conceivable existence of cationic noble gas hydrides containing two Ng atoms. These species have a general formula of HNgFNgH(+) (Ng = He-Xe), and are the cationic counterparts of the neutral HNgF. The optimized geometries, harmonic frequencies, and bonding properties point to ion-dipole complexes between a fluoride anion and two covalent H-Ng(+) cations, best formulated as (H-Ng(+))(2)F-. The HXeFXeH+ is also isoelectronic with the recently experimentally observed HXeOXeH (Khriachtchev et al. J. Am. Chem. Soc. 2008, 130, 6114-6118). The resulting HNgFNgH(+) are thermochemically stable with respect to dissociation into HNg(+) + HNgF and HNg(+) + H + Ng + F, but are largely unstable with respect to both the loss of HNg(+) (with formation of HNg(+) + Ng) and H2F+ (with formation of two Ng atoms). These decompositions pass through bent transition structures, and only the heaviest HAtFArH+, HKrFKrH+, and HXeFXeH+ are protected by energy barriers large enough (ca. 10-15 kcal mol(-1)) to support their conceivable metastability. In line with other series of noble gas compounds, the neon cation HNeFNeH+ is the least stable among the various HNgFNgH(+).