Theoretical analysis of spectra of short polyenes

Orlandi, Giorgio; Zerbetto, Francesco; Zgierski, Marek Z.

doi:10.1021/cr00005a012

Cited by 315 publications

(293 citation statements)

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“…In this work, we have commenced the characterization of the vibrational properties of the simplest member of the family of benzylic amide [2]catenanes. As one might have predicted, in a system of the complexity and the rather low symmetry as the present one, general retrieval of information from the vibrational spectra is not easily accomplished.…”

Section: Resultsmentioning

confidence: 99%

“…Apart from their structures, their characterization in terms of fundamental and induceable properties must perforce start with the study of the electronic and nuclear motions that reflect the different time-scale dynamics present in the system. Here we report the first study of the high-frequency vibrational states of a mechanically interlocked molecule, the benzylic amide [2]catenane 1 (Figure 1). To the best of our knowledge, this is the first vibrational study of any catenane.…”

Section: Introductionmentioning

confidence: 99%

“…Polyenes epitomize this kind of behavior. 2 In contrast, when the building blocks are divided by one or more sp 3 carbon atoms, as is the case with benzylic amide catenanes, perturbation theory can still hold and the molecular properties may be determined by analytical models in both the simplest cases of a "dimer" and even in the most complex case of an infinite chain. Difficultiessand implicitly a degree of interestsarise when the number and the roles of the interacting fragments vary.…”

Section: Introductionmentioning

confidence: 99%

“…The work carried out in this paper presents the results of a combination of experimental and computational, or modeling, techniques aimed at obtaining a picture of the interactions and the high-frequency vibrational dynamics of the simplest octabenzamide [2]catenane, 1. The infrared and Raman spectra are recorded at standard resolution and compared with the result of molecular orbital calculations.…”

Section: Introductionmentioning

confidence: 99%

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High-Frequency Vibrations of the Simplest Benzylic Amide [2]Catenane

Fanti¹,

Fustin²,

Leigh³

et al. 1998

J. Phys. Chem. A

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Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Ricerche, Via Gobetti 101, Bologna, Italy ReceiVed: October 8, 1997; In Final Form: May 5, 1998 Infrared and Raman spectroscopies along with molecular orbital calculations are used to studysfor the first timesthe vibrational motions of a topologically complicated chemical system, namely a [2]catenane of the benzylic amide type. Because of the intrinsic line width of the spectra, comparison of experiments and theory is only partially successful. The insight given by the simulationsswhich show that the CdO normal modes are delocalized while the N-H modes are localizedsis, however, useful and makes us propose a simple model that explains both the larger line width of the spectra of the catenane with respect to those of the parent macrocycle and the great sensitivity of the infrared spectrum of the catenane to the environment. Examples of such sensitivity are the frequency shifts observed upon going from KBr to CsI, features not present in the case of the macrocycle.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

High-Frequency Vibrations of the Simplest Benzylic Amide [2]Catenane

Fanti¹,

Fustin²,

Leigh³

et al. 1998

J. Phys. Chem. A

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“…[1][2][3][4][5][6][7][8] The most significant feature of the electronic structure of all polyenes, except for the shortest ones, stilbene, butadiene, and diphenylbutadiene, is a weakly absorbing excited singlet state S 1 below the strongly absorbing S 2 state. This was first discovered for the case of ␣, -diphenyloctatetraene by Hudson and Kohler.…”

Section: Introductionmentioning

confidence: 99%

Symmetry breaking and spectra of diphenyloctatetraene in n-alkanes

Walser

Zumofen

Plakhotnik

2000

The Journal of Chemical Physics

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Articles you may be interested inElectronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study J. Chem. Phys. 143, 204304 (2015); 10.1063/1.4935578The elusive S 2 state, the S 1/S 2 splitting, and the excimer states of the benzene dimer J. Chem. Phys. 142, 234306 (2015) One-and two-photon excitation spectra, as well as absorption and emission spectra of diphenyloctatetraene ͑DPOT͒ in n-alkanes are investigated at low temperatures. For DPOT in n-octane we report on the measurements of one-photon excitation and emission spectra and for DPOT in n-tetradecane ͑TD͒ on the measurements of one-and two-photon excitation spectra and emission spectra. The spectra are governed by the transitions between the electronic ground (S 0 ) and the two lowest electronic excited singlet states (S 1 ,S 2 ). The interpretation is based on allowed transitions and transitions induced by the S 1 -S 2 coupling due to Herzberg-Teller promoting modes or due to static lattice-induced distortions of DPOT. A single noncentrosymmetric site is observed for DPOT in n-octane. For DPOT in TD a centrosymmetric and a noncentrosymmetric site are reported. The analysis indicates that there is a dynamical equilibrium in the population of these two sites. The experimental data are quantitatively studied by comparison with simulated spectra. The simulation calculations are based on the coupling between nonadiabatic S 1 and S 2 states, harmonic modes, and suitable transition moments and line-shape functions. For DPOT in TD the calculations reveal an interesting interference pattern in the vibronic progressions observed in two-photon excitation spectra.

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Structure of theT1-state wave function of linear polyenes

Takahashi

Watanabe

Kikuchi

1998

Int. J. Quant. Chem.

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Configuration interaction singles CIS calculations of the planar T state 1 of hexatriene, octatetraene, decapentaene, and dodecahexaene showed that the Ž . Ž . HOMO y i ª LUMO q i type single excitations contribute significantly. This is attributed to the similarity of the HOMO, LUMO, and HOMO y i, LUMO q i overlap densities which stem from nodal properties of the molecular orbitals. CASSCF calculations for hexatriene and octatetraene also showed remarkable contributions of the Ž . Ž . HOMO y i ª LUMO q i type singly excited configurations.

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Theoretical analysis of spectra of short polyenes

Cited by 315 publications

References 79 publications

High-Frequency Vibrations of the Simplest Benzylic Amide [2]Catenane

High-Frequency Vibrations of the Simplest Benzylic Amide [2]Catenane

Symmetry breaking and spectra of diphenyloctatetraene in n-alkanes

Structure of theT1-state wave function of linear polyenes

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