Ab Initio Study of the Charge-Transfer Complex of Xenon and Dicarbon

Breidung, Jürgen; Thiel, Walter

doi:10.1006/jmsp.2002.8674

Cited by 4 publications

(6 citation statements)

References 26 publications

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“…The linear C 2 Xe values calculated in this study by BCCD(T)/avtz ( r e = 3.4 Å, Δ E = −47 meV) match well with the BCCD(T)/d-avqz calculations by Breidung and Thiel (3.3 Å, −52 meV) . These values are very different to those reported for the linear C 2 Ar (4 Å and −14 meV) and C 2 Kr (4 Å and −18 meV) complexes. , Indeed, we propose this difference is the reason for unusual spectroscopy of C 2 in solid Xe.…”

Section: Discussionsupporting

confidence: 82%

“…While knowledge of relevant potential energy surfaces (PES) often provide a better spectroscopic understanding, the large number of electrons associated with the Xe atom places a high demand on computational resources. To the authors' knowledge, studies to date have only calculated the C 2 Xe ground-state interaction potential, and no calculations on the excited electronic states have been reported. , While spectroscopy is sensitive to a many-bodied PES, many important questions can be addressed through knowledge of the dopant/host pair potentials only. In this study, we employed the coupled cluster with single, double, and perturbative triple excitations CCSD(T), multiconfiguration self-consistent field (MCSCF), and the Brueckner coupled-cluster method BCCD(T) to this end.…”

Section: Introductionmentioning

confidence: 99%

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Electronic Spectroscopy of C₂ in Solid Rare Gas Matrixes

et al. 2005

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Electronic spectroscopy of the C(2) molecule is investigated in Ar, Kr, and Xe matrixes in the 150-500 nm range. In the Ar matrix, the D ((1)Sigma(u)(+)) <-- ((1)Sigma(g)(+)) Mulliken band near 240 nm is the sole absorption in the UV range, whereas in the Kr matrix additional bands in the 188-209 nm range are assigned to the Kr(n)()(+)C(2)(-) <-- Kr(n)()C(2) charge-transfer absorptions. Because of the formation of a bound C(2)Xe species, the spectral observations in the Xe matrix differ dramatically from the lighter rare gases: the Mulliken band is absent and new bands appear near 300 and 423 nm. The latter is assigned to the forbidden B'((1)Sigma(g)(+)) <-- X ((1)Sigma(g)(+)) transition, but the origin of the former remains unclear. The spectral assignments are aided by electronic structure calculations at the MCSCF, CCSD(T), and BCCD(T) levels of theory and correlation consistent basis sets. A significant presence of multireference character of the C(2)Xe system was noted and a linear ground-state structure is predicted. The computational results contradict previous density functional studies on the same system.

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Section: Discussionsupporting

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Electronic Spectroscopy of C₂ in Solid Rare Gas Matrixes

et al. 2005

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“…The linear structure of C 2 Xe is consistent with electron donation from xenon into the vacant 3σ g -orbital that is oriented along the internuclear axis. [156,157] The computed CϪXe bond length of C 2 Xe (approximately 270 pm) [157] is much shorter than the sum of the van der Waals radii (386 pm) but is significantly longer than the experimental CϪXe bond length in (C 6 F 5 ) 2 Xe (235Ϫ239 pm). [158] Scheme 23.…”

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confidence: 97%

Carbene Complexes of Nonmetals

Kirmse

2005

Eur J Org Chem

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Electrophilic carbenes accept a variety of n‐ and π‐donors. The products range from persistent ylides to matrix‐isolated xenon complexes. Ylides can be viewed as carbene complexes if they regenerate carbenes thermally or undergo concerted methylene transfer reactions. According to these definitions, the present review focuses on oxonium and iodonium ylides. Transient π‐complexes appear to be involved in addition reactions of carbenes with arenes (but not with alkenes). Nucleophilic carbenes form adducts with Lewis acids which are, for the most part, stable and have been well characterized structurally. Only recently attention has been directed to reversible systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…39 Previous work has shown that C 2 Xe has a linear geometry. 35 Both a linear and a bent structure were considered for C 3 Xe. Geometries were optimized using ab initio MP2 theory with a LJ18 basis set for Xe 34 and a 6-311þþG (2d,2p) basis set for carbon.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…34 Calculations on other Xe-inserted molecules, such as HXeCN and HXeNC, support the experimental observations well. 24 Following the observation of the C 2 Xe species, high level ab initio calculations for C 2 Xe were reported 35 and showed that C 2 Xe has a linear structure with a rather flat potential surface. This flatness causes an uncertainty in the length of the C-Xe bond.…”

Section: Introductionmentioning

confidence: 99%