Interaction of the Vibrational and Electronic Motions in Some Simple Conjugated Hydrocarbons

Liehr, Andrew D.

doi:10.1515/zna-1958-0601

Cited by 15 publications

(2 citation statements)

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“…The established dominance of the vx vibration in all our spectra indicates that the radiative deactivation of TI of all the molecules investigated proceeds in a similar way as for benzene derivatives. Thus the TI states of all these molecules should possess mainly benzenoid character and may be assigned to a 'B2('ir,'ir*) state (Liehr, 1961;Moffit and Liehr, 1957). This is affirmed by the fact that the energy of the TI -+ So transitions of all the molecules agrees well with results of a SCF-LCAO-MO calculation for 1.2 dihydroxy and 1,2 dimethoxybenzenes, respectively (Forsen and Alm, 1965).…”

Section: Discussionsupporting

confidence: 65%

The Lowest Excited Triplet States of Codeine and Morphine and of Their Molecular Subunits Veratrole and Guaiacol

Slama

Basché

Bräuchle

et al. 1988

Photochem & Photobiology

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Abstract— The lowest excited triplet T1 states of the two alkaloids, morphine and codeine, have been investigated by ODMR and emission spectroscopy. The electronic character of their T1 states could be determined by comparing the T1 properties with those of the constituent parts guaiacol and veratrole. The T1 properties, e.g. phosphorescence spectra, zero‐field splitting parameters and triplet sublevel selective decay rates are very similar for the constituent parts and the alkaloids. Thus, in analogy to veratrole and guaiacol, the T1 state of codeine and morphine is assigned to a ππ* state mainly localized on the benzene ring and the attached alkoxy and hydroxy groups. There is no evidence for a contribution from the other subunits, trialkylamine and unsaturated alcohol, to the T1 state of codeine and morphine.

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Section: Discussionsupporting

confidence: 65%

The Lowest Excited Triplet States of Codeine and Morphine and of Their Molecular Subunits Veratrole and Guaiacol

Slama

Basché

Bräuchle

et al. 1988

Photochem & Photobiology

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“…A Jablonski diagram illustrates these transitions in figure 1. These mechanisms include vibronic mixing, singlet-state mixing, and perturbations that lend some of their energy to make T 1 →S 0 transitions partially allowed [18][19][20]. Since the singlet and triplet electronic state have orthogonal symmetries, the T 1 →S 0 transition moment orientation is typically different (orthogonal) from the S 1 →S 0 transition moment orientation [21][22][23] and the observed polarization of phosphorescence is negative or very close to zero.…”

Section: Introductionmentioning

confidence: 99%

Photophysical properties of 2-Phenylindole in poly (vinyl alcohol) film at room temperature. Enhanced phosphorescence anisotropy with direct triplet state excitation

Gryczyński

Kimball

Fudala

et al. 2020

Methods Appl. Fluoresc.

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We report the spectral properties of 2-Phenylindole (2PI) embedded in rigid poly (vinyl alcohol) (PVA) film. The 2PI in PVA film shows relatively strong and structured fluorescence with a maximum at 370 nm and surprisingly strong room temperature phosphorescence with an emission maximum of about 500 nm. The dye is highly immobilized in the polymer matrix, thus presenting high fluorescence anisotropy in an isotropic film of about 0.3 at room temperature. The 2-Phenylindole phosphorescence excited in the usual way through the electronic singlet state excitation (S0 → S1 absorption) results in a very low, near zero anisotropy. We now report that we can directly excite the dye to the triplet state T1 and observe high phosphorescence anisotropy similar to the fluorescence anisotropy. The extinction coefficient for S0 → T1 absorption in the PVA matrix is unusually high- only about 3 orders of magnitude lower than S0 → S1 absorption. We consider this direct excitation to indole’s triplet state a very significant finding that may lead to many practical applications. The unusually long-wavelength of excitation around 400 nm, much above typical UV absorption, results in a high phosphorescence anisotropy. This provides a new way to study rotational motion of larger biological objects in the microsecond time scale not accessible through typical fluorescence studies.

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Quasi-Equilibrium Theory of Mass Spectra

Rosenstock

Krauß

1963

Mass Spectrometry of Organic Ions

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Interaction of the Vibrational and Electronic Motions in Some Simple Conjugated Hydrocarbons

Abstract: Die in der Theorie der Wechselwirkungen zwischen den Schwingungs- und Elektronenbewegungen in konjugierten Kohlenwasserstoffen vorkommenden Integrale werden algebraisch und numerisch berechnet.

Cited by 15 publications

References 1 publication

The Lowest Excited Triplet States of Codeine and Morphine and of Their Molecular Subunits Veratrole and Guaiacol

The Lowest Excited Triplet States of Codeine and Morphine and of Their Molecular Subunits Veratrole and Guaiacol

Photophysical properties of 2-Phenylindole in poly (vinyl alcohol) film at room temperature. Enhanced phosphorescence anisotropy with direct triplet state excitation

Quasi-Equilibrium Theory of Mass Spectra

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