Diatomics-in-molecules study of the photoabsorption spectra of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si22.gif" overflow="scroll"><mml:mrow><mml:msubsup><mml:mrow><mml:mi mathvariant="normal">Xe</mml:mi></mml:mrow><mml:mrow><mml:mi>n</mml:mi></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math> clusters

Kalus, René; Hrivňák, Daniel; Paška, Petr

doi:10.1016/j.chemphys.2004.11.007

Cited by 9 publications

(6 citation statements)

References 23 publications

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“…Kalus et al. have calculated that 12–18 additional xenon atoms are needed to stabilize a linear symmetric Xe 4 + unit, with the outer xenon atoms at a distance of about 440 pm from the Xe 4 + core 4d–f. UV/Vis spectra of those clusters in the molecular beam experiment indeed show a bathochromic shift of the absorption with increasing size of the cluster.…”

Section: Calculated Equilibrium Bond Lengths and Harmonic Vibrationalmentioning

confidence: 99%

The Blue Xe₄⁺ Cation: Experimental Detection and Theoretical Characterization

Seidel¹,

Seppelt²,

Wüllen³

2007

Angew Chem Int Ed

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Section: Calculated Equilibrium Bond Lengths and Harmonic Vibrationalmentioning

confidence: 99%

The Blue Xe₄⁺ Cation: Experimental Detection and Theoretical Characterization

Seidel¹,

Seppelt²,

Wüllen³

2007

Angew Chem Int Ed

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“…3͒ and of the photoabsoption cross section of Xe n + clusters. 7 These results indicate that, compared to the DIM geometries, the LDA overestimates considerably the bond lengths ͑with the exception of the b 1 bond in Xe 4 + ͒. As for the GGA, it produces larger bond lengths than the LDA.…”

Section: Resultsmentioning

confidence: 83%

“…These results were confirmed by further experimental evidence and by theoretical calculations of the photoabsorption of cationic xenon clusters. [4][5][6][7] Up to now, most theoretical studies of cationic xenon clusters made use of semiempirical methods, especially the "diatomics in molecules" ͑DIM͒ approach. The DIM method 8 has been quite successful in describing Xe clusters, both for the ground state 3,5 and their optical absorption.…”

Section: Introductionmentioning

confidence: 99%

“…The DIM method 8 has been quite successful in describing Xe clusters, both for the ground state 3,5 and their optical absorption. 6,7 In this approach, a model Hamiltonian is built using high quality ab initio diatomic data, such as energy surfaces of the neutral and the cationic dimer, both in the ground state and first excited state. Several extensions to the DIM model are required in order to accurately describe the electronic properties of cationic xenon clusters.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Photoabsorption spectra of small cationic xenon clusters from time-dependent density functional theory

Oliveira¹,

Nogueira²,

Marques³

et al. 2009

The Journal of Chemical Physics

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Upon ionization, rare-gas (like Ar and Xe) clusters shift their absorption spectrum from the ultraviolet to the visible. This happens as bonding becomes much stronger due to the removal of an electron from a strongly antibonding orbital. In this article, we study the absorption spectrum of small cationic xenon clusters (Xe(n) (+), with n=3,...,35) by means of time-dependent density functional theory. These calculations include relativistic effects through the use of relativistic j-dependent pseudopotentials in a two-spinor formulation of the Kohn-Sham equations. The peak positions in our calculated spectra are in fairly good agreement with experiment and confirm that absorption is mainly due to a charged linear core composed of 3, 4, or 5 Xe atoms where the positive charge is localized. However, we find large deviations concerning the oscillator strengths, which can be partially explained by the unsatisfactory treatment of exchange in common density functionals. Furthermore, we find that adequate ground-state geometries are necessary for the correct prediction of the qualitative features of the spectra.

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“…Kalus et al. haben berechnet, dass 12–18 zusätzliche Xenonatome benötigt werden, um einen linear symmetrischen Xe 4 + ‐Kern zu stabilisieren, wobei die äußeren Xenonatome etwa 440 pm vom Kern entfernt sind 4d–f. UV/Vis‐Spektren dieser Cluster im Molekularstrahlexperiment zeigen in der Tat eine Verschiebung zu größeren Wellenzahlen mit wachsender Clustergröße.…”

Section: Berechnete Gleichgewichtsabstände (Re) Harmonische Frequenzunclassified