The experimental electronic and vibrational spectra of fulvene

Brown, R. D.; Domaille, PJ; Kent, JE

doi:10.1071/ch9701707

Cited by 35 publications

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“…2,4 This good agreement stems from the fact that the lowest two excited singlet states of fulvene are valence states, hence they are very reasonably described without inclusion of diffuse orbitals and dynamical correlation. It turns out that the C 2v configuration of the S 1 state is unstable against the out-of-plane CCH 2 torsion and CH 2 wag ͑vide infra͒.…”

Section: Electronic States and Geometriesmentioning

confidence: 74%

“…Its ultraviolet ͑UV͒ electronic spectra were reported on several occasions 1,2,4,5 and their vibronic structure discussed. 2,5 Three electronic transitions were discerned in the energy region between 510 and 180 nm. The first weakly allowed transition ( f ϭ0.008) was assigned as the S 0 (A g )→S 1 (1B 2 ).…”

Section: Introductionmentioning

confidence: 99%

“…5 The second electronic transition in the absorption spectrum, at ϳ37 500 cm Ϫ1 ͑267 nm͒ is quite strong ( f ϭ0.34) and it is assigned as 1A 1 →2A 1 . 2 Its structure consists of a strong long ͑20 members͒ progression with mean separation of ϳ495 cm Ϫ1 and a shorter weak progression with similar spacing. These progressions were again assigned to an out-of-plane vibrational motion, namely the CH 2 deformation of b 1 symmetry.…”

Section: Introductionmentioning

confidence: 99%

“…These progressions were again assigned to an out-of-plane vibrational motion, namely the CH 2 deformation of b 1 symmetry. 2,6 The third electronic transition is also strong and starts at 47 590 cm Ϫ1 ͑202 nm͒. 2 It was assigned as a Rydberg 1A 1 ←B 1 (3s) transition, 4 its structure being prone to external perturbations.…”

Section: Introductionmentioning

confidence: 99%

“…2,6 The third electronic transition is also strong and starts at 47 590 cm Ϫ1 ͑202 nm͒. 2 It was assigned as a Rydberg 1A 1 ←B 1 (3s) transition, 4 its structure being prone to external perturbations. In vapor phase this structure resembles the low energy part of the structure of the S 0 →S 1 transition except for a much stronger 0-0 band.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical analysis of vibronic structure of absorption spectrum of fulvene

Negri

Zgierski

1995

The Journal of Chemical Physics

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Ab initio and semiempirical quantum-chemical methods are used to study the lowest two valence excited states of fulvene. A new assignment is proposed for ground state frequencies and the Franck-Condon structure of the S 0 →S 1 , S 2 transitions is obtained with the help of calculated geometries and vibrational force-fields of the electronic states involved. It is shown to account very satisfactorily for the observed vibronic structure of the absorption spectra of fulvene. It is demonstrated that, contrary to previous assumptions, CH 2 out-of-plane vibrational modes play no role in formation of the vibronic structures of the two transitions.

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Section: Electronic States and Geometriesmentioning

confidence: 74%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Theoretical analysis of vibronic structure of absorption spectrum of fulvene

Negri

Zgierski

1995

The Journal of Chemical Physics

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Intra and interatomic energy contributions in the photophysical relaxation of small aromatic molecules

Jara‐Cortés,

Pérez‐Pimienta,

Park

et al. 2024

ChemPhotoChem

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A theoretical study of the non‐radiative photophysical relaxation mechanisms of the first singlet excited state of benzene, cyclobutadiene and fulvene is presented. For these molecules, the calculation of the Minimum Energy Path (MEP) leading from the Franck‐Condon region to the surface crossing with the ground state is carried out. Subsequently, the decomposition of the electronic energies into atomic and pair contributions is performed using the Interacting Quantum Atom (IQA) method. The IQA approach provides the important mechanistic information necessary to rationalise some relevant aspects of the processes, such as the components that explain the appearance of an energy barrier or that favour the crossing between potential energy surfaces (PES); it also allows to quantify the direct effect on the MEP due to the inclusion of a substituent. In particular, it is shown how the IQA energies allow measuring the extent to which the formation of biradicaloid structures affects the crossing of the PES. The analysis of electron density functions suggest that aromaticity is not a driving force on the relaxation processes. Overall, this work shows the potential of the IQA method as a useful tool for the detailed description of photophysical processes.

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Photoelectron‐Spectroscopic Evidence for the Orbital Sequence in Fulvene and 3, 4‐Dimethylene‐cyclobutene

Heilbronner

Gleiter

Hopf

et al. 1971

Helvetica Chimica Acta

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Summary. The photoelectron spectra of fulvene (11) and of 3,4-dimethylene-cyclobutene (111) have been recorded. The PE. bands are correlated, in order of increasing ionisation potentials, with the following orbitals: 11: la&), 2b,(n), 7b,(a), lb,(n); 111: 2b1(n). la,@), 10a,(o), 8b,(o), lb,(n). This assignment is based on a semi-quantitative perturbation MO-model and on the SCF-LCAO-MO calculations reported by Praud, Millie & Berthiev [5] for benzene, I1 and 111. There are four ways in which an ethylene moiety can be formally connected with a s-cis-butadiene part to yield a planar, nionocyclic o, n-system containing a t least one additional plane of symmetry perpendicular to the o-framework : benzene (I), fulvene (11), 3,4-diniethylene-cyclobutene (111) and trisniethylene-cyclopropane = !3]radialene (IV). Of these, I1 [2] and I11 r3] are the two isoelectronic isomers of I, which in the past have attracted the greatest interest. Like benzene they are planar and possess a conjugated n-system containing six electrons, I1 being a non-alternant and I11 an alternant cross-conjugated hydrocarbon. As a consequence, they are ideal test cases for n-theories, and numerous calculations on all levels of sophistication have been performed to explain their physical and chemical properties 141 151. ( E , is the total n-electron energy according to a standard HMO-calculation)The photoelectron spectra (PE. spectra) of I1 and 111 are shown in Fig. I a n d the corresponding verticai ionisation potentials 1" are collected in Table 3 .The spectra have been recorded on a modified PS 15 photoelectron Tunzer-type spectrometer [6] of ~~~~~~~~~Elmer Lld. (Beaconsfield, England). For experimental details the reader is referred to previous communications of this series, ~. g .[7]. Institut fur Organische Chemie der Universitat Karlsruhe. Organiscli-chemisches Institut der Universitat Gottingen. 784HELVETICA CHIMICA ACTA -Vol. 54, Fasc. 3 (1971) -Nr. 78 An assignment of the PE. spectra can be obtained by labelling each band according to the molecular orbital qjJ from which the electron is thought to be ejected when the moleculc M is ionised:'Tablc 1. Photoelectroiz spectra of beizzene ( I ) , f-ulvewe ( I I ) aizd 3,4-dimethylene-cyclobutene ( I 11) All values (in cV) refer to vertical ionisation potentials I v . The nuinbcring corresponds to the one g i w n in Fig. 1. Values in brackets refer t o prominent fine-structure components of lower intensity Orb.Char. A criterion for the validity of the assignment will be its conipatibility with the assignments of PE. spectra of other similar molecules, based on the same MO-model. Unfortunately the vibrational pattern of the individual PE. bands in the spectra of I1 and 111, shown in Fig. 1, is not sufficiently well resolved to provide an additional check of the assignment, through an analysis of the spacing and intensity of the individual progression components 1-91 (see j-101 in the case of I). I vTo begin with, we sliall first estalilish wliicli of the bands in the PE. spectra of I1 a...

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The experimental electronic and vibrational spectra of fulvene

Cited by 35 publications

References 0 publications

Theoretical analysis of vibronic structure of absorption spectrum of fulvene

Theoretical analysis of vibronic structure of absorption spectrum of fulvene

Intra and interatomic energy contributions in the photophysical relaxation of small aromatic molecules

Photoelectron‐Spectroscopic Evidence for the Orbital Sequence in Fulvene and 3, 4‐Dimethylene‐cyclobutene

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