The Rydberg Doublets of Ethylene; Intensity Stealing in Mono-Olefins

Watson, F. H.; Nycum, M. W.

doi:10.1080/00387017508067325

Cited by 8 publications

(7 citation statements)

References 22 publications

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“…[66][67][68][69] On the basis of the assignment of nontotally symmetric vibrational activity in the absorption spectra of other monoolefins, 31,64 as well as on considerations of observed and calculated oscillator strengths, it has previously been suggested that the (π,3s) transition in these compounds is partly vibronically induced via coupling to the (π,π*) valence state. 15,30,31,64 Unfortunately, the present (1+1) excitation spectrum of the (π,3s) does not allow such a detailed vibrational analysis that would be able to corroborate such a suggestion also for TME.…”

Section: B Rydberg Excitations In Tetramethylethylenementioning

confidence: 67%

“…Several assignments have been put forward in the literature to explain the presence of two strong electronic transitions. 10,11,[13][14][15][16] Although it is clear that one of the two states is the (π,π*) valence state, even its spectral location has been subject of debate. In the early work by Snyder and Clark, 10 the band at 55000 cm -1 was assigned to the (π,π*) valence state, an assignment that was sustained in later studies on steroids by Yogev et al 13 and in ab initio studies by Watson et al 15 However, the assignment of the band at 48000 cm -1 remained matter of debate.…”

Section: Introductionmentioning

confidence: 99%

“…10 This was supported by Yogev et al, 13 but they also proposed an alternative assignment based upon the concept of Rydberg-valence mixing between the (π,π*) valence state and the (π,3p y ) Rydberg state as has been extensively advocated by Peyerimhoff et al for ethylene. [17][18][19] Watson et al 15 reached the conclusion in their theoretical studies on ethylene that the band at 48000 cm -1 corresponds to a vibronically induced transition to the (π,3s) Rydberg state coupled to the (π,π*) valence state. An entirely different assignment for the (π,π*) valence state was first suggested by Allan et al in their studies on the excited states of BCH.…”

Section: Introductionmentioning

confidence: 99%

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Isolated Building Blocks of Photonic Materials: High-Resolution Excited-State Photoelectron Spectroscopy of Jet-Cooled Tetramethylethylene and 1,1‘-Bicyclohexylidene

Rijkenberg¹,

Buma²,

Walree³

et al. 2002

J. Phys. Chem. A

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The spectroscopy and photophysics of tetramethylethylene and 1,1‘-bicyclohexylidene have been investigated using excited-state photoelectron spectroscopy in combination with multiphoton excitation. Vibronic coupling within the full manifold of the excited singlet states has been shown to play a dominant role in determining the spectroscopic properties of these compounds. Although this vibronic coupling inhibits the determination of excited state excitation energies by excitation spectroscopy, it enables at the same time their observation in the photoelectron spectra. As a result, a large number of previously unobserved Rydberg states could be located and assigned. For both molecules ionization from the Rydberg states is observed to be heavily perturbed by ionization from the underlying quasi-continuum of the (π,π*) valence state. The photoelectron spectra of 1,1‘-bicyclohexylidene reveal that the state around 55000 cm-1 (6.82 eV), which has previously been assigned as a second valence state, does not show the ionization pattern expected on the basis of previous suggestions made for the character of this state. On the basis of this observation, configuration mixing between the (π,π*) valence state and the (π,3d) Rydberg manifold is offered as a possible explanation.

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Section: B Rydberg Excitations In Tetramethylethylenementioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Isolated Building Blocks of Photonic Materials: High-Resolution Excited-State Photoelectron Spectroscopy of Jet-Cooled Tetramethylethylene and 1,1‘-Bicyclohexylidene

Rijkenberg¹,

Buma²,

Walree³

et al. 2002

J. Phys. Chem. A

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“…These two bands remain discernible both in solution and the solid state,1,10,11 an observation that has been interpreted as giving evidence for their valence character. Efforts to assign the two low‐lying “valence” excitations have led to widely varying assignments 5–7, 10–13. Elucidation of the nature and properties of these excited states is important for various reasons.…”

Section: Cis Calculated Vertical Excitation Energies [Ev] and Oscillamentioning

confidence: 99%

Rydberg–Valence Interactions in Monoolefins: Dispersing Electronic Properties in 1,1′‐Bicyclohexylidene

et al. 2002

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Disentangling the embrace: Calculations on the electronic structure of 1,1′‐bicyclohexylidene (shown in the graphic) indicate that electronic coupling of the excited ππ* valence state with Rydberg states lies at the basis of the hitherto poorly understood presence of two low‐lying electronic states with valencelike properties. States with similar characteristics are predicted for the entire class of monoolefins.

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“…This interpretation, while generally accepted, has always led to difficulties. 1,[8][9][10][11][12][13][14][15] Obtaining agreement between theory and experiment for ethylene has proved to be difficult and illusive. Therefore, as soon as a new experimental method became available, it was utilized with the hope of furthering the understanding of the electronic structure of ethylene.…”

Section: Introductionmentioning

confidence: 99%

Ethylene. Experimental Evidence for New Assignments of Electronic Transitions in the π → π* Energy Region. Absorption and Magnetic Circular Dichroism Measurements with Synchrotron Radiation

2004

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An exploration of the vacuum ultraviolet magnetic circular dichroism and absorption spectra of propylene and a comparison to ethylene spectra provides new information on the electronic structure of ethylene. Ethylene has three electronic transitions in the energy region previously assigned as two. The presently proposed assignments for these transitions are π → 3s(1Ag → 1B3u), π → π*(1Ag → 1B1u), and π → 3p. The lowest energy transition that was previously assigned as the beginning of the π → π* is assigned as the π → 3s transition. The π → π* and π → 3p transitions are accidentally degenerate in ethylene. The electronic transition with sharp structure doublets which was previously assigned as π → 3s is assigned as one of the π → 3p [π → 3pσ (1Ag → 1B2g), π → 3p y (1Ag → 1B1g), or π → 3p x (1Ag → 1A1g)] vibronically allowed electronic transitions. A case is presented that it is the π → 3pσ (1Ag → 1B2g) and/or the π → 3p y (1Ag → 1B1g) electronic transitions that are responsible for the sharp structured doublets in ethylene.

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The Rydberg Doublets of Ethylene; Intensity Stealing in Mono-Olefins

Cited by 8 publications

References 22 publications

Isolated Building Blocks of Photonic Materials: High-Resolution Excited-State Photoelectron Spectroscopy of Jet-Cooled Tetramethylethylene and 1,1‘-Bicyclohexylidene

Isolated Building Blocks of Photonic Materials: High-Resolution Excited-State Photoelectron Spectroscopy of Jet-Cooled Tetramethylethylene and 1,1‘-Bicyclohexylidene

Rydberg–Valence Interactions in Monoolefins: Dispersing Electronic Properties in 1,1′‐Bicyclohexylidene

Ethylene. Experimental Evidence for New Assignments of Electronic Transitions in the π → π* Energy Region. Absorption and Magnetic Circular Dichroism Measurements with Synchrotron Radiation

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