Charge transfer states of C2 in Kr clusters

Fiedler, Steven L.; Kunttu, Henrik; Eloranta, Jussi

doi:10.1016/j.chemphys.2004.04.031

Cited by 1 publication

(8 citation statements)

References 24 publications

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“…The extracted energy difference from the experimental spectra is 0.63 eV, which is close to the theoretically predicted value of 0.59 eV. Furthermore, the observed band structure compares well with our previous theoretical predictions . On the basis of these arguments, we assign the 188−209 nm bands to Kr n + C 2 - ← Kr n C 2 CT absorptions.…”

Section: Discussionsupporting

confidence: 88%

“…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. If the trapping cavity size in Xe lattice is larger than the r e of C 2 Xe, the C 2 dopant would be expected to be asymmetrically centered within the cavity.…”

Section: Discussionsupporting

confidence: 82%

“…Experimentally, we have recorded the UV absorption of acetylene photofragments in Ar, Kr, and Xe matrixes. For the Kr matrix, a previously unreported set of bands in the 188−209 nm region was found to belong to the same absorber, and by comparison of the spectrum to that of Cl and CN doped Kr matrixes and by theoretical predictions, the band set has been assigned to the C 2 Kr n neutral to C 2 - Kr n + charge-transfer transitions. , …”

Section: Discussionmentioning

confidence: 84%

“…This observation served as our motivation to extend our studies to another very similar electron acceptor, the C 2 molecule, which has electron affinity similar to Cl atom and CN radical. In a previous report, we presented DIIS predictions of the charge-transfer absorptions of C 2 doped Kr clusters of various size . In this paper, we show the UV absorption spectra of extensively photolyzed acetylene doped Ar, Kr, and Xe matrixes down to 150 nm.…”

Section: Introductionmentioning

confidence: 86%

“…In a previous report, we presented DIIS predictions of the charge-transfer absorptions of C 2 doped Kr clusters of various size. 8 In this paper, we show the UV absorption spectra of extensively photolyzed acetylene doped Ar, Kr, and Xe matrixes down to 150 nm. It will be shown that charge-transfer bands can be confidently assigned only in Kr matrix.…”

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: 88%