Rydberg and Valence States in the Tetra-atomic Molecules B2H2, C2H2 and C2H2+

Perić, Miljenko; Peyerimhoff, Sigrid D.

doi:10.1007/0-306-46938-3_6

Cited by 3 publications

(9 citation statements)

References 117 publications

(110 reference statements)

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“…A comprehensive review of the excited singlet electronic states of C 2 H 2 up to 1999 has been presented by Peric and Peyrimhoff, including experimental and theoretical investigations. A short updated summary is given below.…”

Section: Resultsmentioning

confidence: 99%

“…All calculations were performed with the program MOLPRO running on the HP-XC 4000 cluster of the ULB/VUB computing center, using the internally contracted multireference configuration interaction method (CMRCI) and extended basis sets. It is particularly important , to devote special care to the choice of both the one- and N -electron basis sets when dealing with a mixed Rydberg−valence region, as is the case around 9 eV for acetylene. This requires the use of an extended basis set including atomic-like n l diffuse functions suitable to represent the Rydberg orbitals of the molecular system.…”

Section: Methodsmentioning

confidence: 99%

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Revisiting Mulliken’s Concepts about Rydberg States and Rydberg−Valence Interactions from Large-Scale Ab Initio Calculations on the Acetylene Molecule

et al. 2009

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A quantitative characterization of the Rydberg and valence singlet electronic states of acetylene lying in the 5-10.7 eV region is performed by using large-scale ab initio calculations. A special attention is paid on the comparison between the present calculations and Mulliken's concepts for Rydberg states, based on single-electron and single-configuration description. Most of the properties of the Rydberg states have been qualitatively understood via this comparison, mainly shown by the shape and size of the outer Rydberg molecular orbital. More quantitatively, Rydberg-valence mixing has been evaluated in several excited energy regions, as for instance, the interaction between the ' (1pig)2 1Ag doubly excited valence state and the manifold of electronic components of the np series, or the interaction between the 1pig 1Bu valence state and the 3dpig 1Sigma(u)+ Rydberg state. The rapid predissociation of the lowest 3s(sigma) 1Piu Rydberg state has been interpreted as a case of Rydbergization, earlier predicted by Mulliken.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Revisiting Mulliken’s Concepts about Rydberg States and Rydberg−Valence Interactions from Large-Scale Ab Initio Calculations on the Acetylene Molecule

et al. 2009

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“…The upper state of the 84 845 cm –1 band is located at a higher energy region than the 4pπ 1 Σ g + state and at a lower energy region than the 5pπ 1 Δ state. Ab initio calculations predict that the singlet members of the n p complex are n pσ 1 Π g , n pπ 1 Δ g , n pπ 1 Σ g – , and n pπ 1 Σ g + in increasing energy order. ,, These facts indicate that the upper state of the 84 845 cm –1 band is the 0° level of the 5pσ 1 Π g state. Recent large-scale ab initio CMRCI calculations predict that the adiabatic energy of the 5pσ 1 Π g state is 85 604 cm –1 , which is close to the experimental value of 84 845 cm –1 .…”

Section: Resultsmentioning

confidence: 94%

“…Rydberg states of simple molecules such as acetylene, which have been investigated by many researchers for a long time, are subjects for study of the Rydberg–valence interactions because many crucial issues remain unresolved. In the lowest n = 3 Ry states of acetylene, six Rydberg series that converge on the first ionization potential are expected; the six Rydberg series emerge as a result of electron promotion from π u to n sσ g , n pσ u , n pπ u , n dσ g , n dπ g , and n dδ g orbitals, and these electron configurations result in 11 singlet electronic states …”

Section: Introductionmentioning

confidence: 99%

“…The Renner–Teller effect and Rydberg–valence interaction of acetylene have been important topics for theoretical studies ,− because these interactions influence the dynamic behavior of molecules in low Rydberg states. The excitation energies of Rydberg states have been accurately predicted using ab initio outer valence Green functions (OVGF) and contracted multireference configuration interaction (CMRCI) …”

Section: Introductionmentioning

confidence: 99%

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Analysis of Low-Lying Gerade Rydberg States of Acetylene Using Two-Photon Resonance Fluorescence Excitation Spectroscopy

et al. 2013

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The np gerade Rydberg states of acetylene were analyzed using two-photon resonance fluorescence excitation spectroscopy in the 72,000-93,000 cm(-1) energy region. The npπ(1)Σ(g)(+) and npπ(1)Δ(g) Rydberg series (n = 3-5) were identified in the fluorescence excitation spectrum measured by monitoring the C(2) d(3)Π(g)-a(3)Π(u) Swan system. Some vibronic bands were assigned to the npπ(1)Δ(g)-X̃(1)Σ(g)(+) transition on the basis of rotational analysis. The 5pσ(1)Π(g) state was observed, which is the first such observation in an npσ(1)Π(g) series. Rotational analysis of the 5pσ(1)Π(g)-X̃(1)Σ(g)(+) transition showed e/f-symmetry dependent predissociation of acetylene in the 5pσ(1)Π(g) state. The 0(0)(0) band of the deuterated acetylene (C(2)D(2)) 4pπ(1)Σ(g)(+)-X̃(1)Σ(g)(+) transition exhibits an atypical structure, which was satisfactorily reproduced by a simple model of quantum interference between the discrete and quasi-continuum states. The predissociative lifetimes of the npπgerade Rydberg states were estimated from the spectral profiles. The predissociation mechanism of acetylene in the Rydberg states is discussed.

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Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases: Unravelling the Dichotomy

de Azevedo Santos,

Trujillo‐González,

Jiménez‐Halla

et al. 2023

Chemistry A European J

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We have quantum chemically investigated the boron–boron bonds in B2, diborynes B2L2, and diborenes B2H2L2 (L = none, OH2, NH3) using dispersion‐corrected relativistic density functional theory at ZORA‐BLYP‐D3(BJ)/TZ2P. B2 has effectively a single B–B bond provided by two half π bonds, whereas B2H2 has effectively a double B=B bond provided by two half π bonds and one σ 2p‐2p bond. This different electronic structure causes B2 and B2H2 to react differently to the addition of ligands. Thus, in B2L2, electron‐donating ligands shorten and strengthen the boron–boron bond whereas, in B2H2L2, they lengthen and weaken the boron–boron bond. The aforementioned variations in boron–boron bond length and strength become more pronounced as the Lewis basicity of the ligands L increases.

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Rydberg and Valence States in the Tetra-atomic Molecules B2H2, C2H2 and C2H2+

Cited by 3 publications

References 117 publications

Revisiting Mulliken’s Concepts about Rydberg States and Rydberg−Valence Interactions from Large-Scale Ab Initio Calculations on the Acetylene Molecule

Revisiting Mulliken’s Concepts about Rydberg States and Rydberg−Valence Interactions from Large-Scale Ab Initio Calculations on the Acetylene Molecule

Analysis of Low-Lying Gerade Rydberg States of Acetylene Using Two-Photon Resonance Fluorescence Excitation Spectroscopy

Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases: Unravelling the Dichotomy

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