Sensitized phosphorescence in organic solutions at low temperature. Energy transfer between triplet states

Terenin, A.; Ермолаев, В. Л.

doi:10.1039/tf9565201042

Cited by 202 publications

(66 citation statements)

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“…Since the first report by Terenin and Ermolaev, benzophenone (BP)/naphthalene (NP) systems have been widely used as models to study inter-and intra-molecular singletsinglet and triplet-triplet energy transfer processes [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Thus, Shizuka and coworkers have intensively investigated the sensitization of the NP triplet by BP, the behavior of the triplet-excited states of BP and NP and their interactions.…”

Section: Introductionmentioning

confidence: 99%

Fast transient absorption spectroscopy of the early events in photoexcited chiral benzophenone–naphthalene dyads

Pérez‐Ruiz¹,

Groeneveld²,

Stokkum³

et al. 2006

Chemical Physics Letters

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General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. Download date: 10 May 2018This article was originally published in a journal published by Elsevier, and the attached copy is provided by Elsevier for the author's benefit and for the benefit of the author's institution, for non-commercial research and educational use including without limitation use in instruction at your institution, sending it to specific colleagues that you know, and providing a copy to your institution's administrator. All other uses, reproduction and distribution, including without AbstractPhotoinduced intra-molecular energy transfer in two ketoprofen(KP)-naproxol(NPX) diastereomers proceeds via two pathways. Very fast singlet-triplet energy transfer (k = 1.2 · 10 11 s À1 ) from KP to NPX occurs for a small percentage (6%) and the major pathway is triplet-triplet energy transfer (k $ 3 · 10 9 s À1 ). This was shown with femtosecond transient absorption spectroscopy and global and target analysis. Whereas the NPX triplet decay is strongly stereospecific (ratio of 1.6), the NPX triplet state formation for both dyads is very similar (ratio of 1 for the fast process and 1.2 for the slower process).

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Section: Introductionmentioning

confidence: 99%

Fast transient absorption spectroscopy of the early events in photoexcited chiral benzophenone–naphthalene dyads

Pérez‐Ruiz¹,

Groeneveld²,

Stokkum³

et al. 2006

Chemical Physics Letters

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“…Since the excitation of the acceptor S 0 state takes place from a configuration close to the equilibrium position where the gradient is negligible, the g value corresponds essentially to the gradient of the triplet state surface, only ͓gӍg(T 1 )ϵg 1 ͔. According to this, the acceptor excitation energy in the new basis set depends only on a single coordinate 1 A , which is that of the triplet acceptor gradient vector:…”

Section: ͑14͒mentioning

confidence: 99%

“…This expression can also be redefined in a new basis set, in which the coordinates are 1 A and those, for the acceptor only, diagonalizing the Hessian matrix of the energy in the subspace of coordinates orthogonal to 1 A , that is, i A with iϭ2,...,3N A Ϫ6. If the donor coordinates q i D are preserved, we have…”

Section: ͑17͒mentioning

confidence: 99%

“…͑22͒ can now be analyzed in detail based on the properties of the abovediscussed PES. Thus, the relative velocity v with which the complex crosses the coupling space would be determined by the vibrational frequency of the modes contained in 1 . Since in the model discussed here the GD vector depends only on the properties of the acceptor PES ͑or, in other words, the decrease in excitation energy is due only to the acceptor deformation͒, the value of v would depend on the acceptor vibrational frequencies, as well as on the effect of the solvent vibrational modes coupled to that of the supermolecule and temperature.…”

Section: ͑22͒mentioning

confidence: 99%

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A theory ofnonverticaltriplet energy transfer in terms of accurate potential energy surfaces: The transfer reaction from π,π* triplet donors to 1,3,5,7-cyclooctatetraene

Frutos

Castaño

Andrés

et al. 2004

The Journal of Chemical Physics

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Triplet energy transfer ͑TET͒ from aromatic donors to 1,3,5,7-cyclooctatetraene ͑COT͒ is an extreme case of ''nonvertical'' behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated ͑Arrhenius͒ process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces ͑PES͒ of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion parameter ␥ϭ(2g 2 / 1 ) 1/2 in which g stands for the norm of the energy gradient in the PES of the acceptor triplet state and 1 is a combination of vibrational force constants of the ground-state acceptor in the gradient direction. The application of the model to existing experimental data for the triplet energy transfer reaction to COT from a series of , * triplet donors, provides a detailed interpretation of the parameters that determine the transfer rate constant. In addition, the model shows that the observed decrease of the acceptor electronic excitation energy is due to thermal activation of CvC bond stretchings and C-C bond torsions, which collectively change the ground-state COT bent conformation (D 2d ) toward a planar triplet state (D 8h ).

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“…J. Chem. Downloaded from www.nrcresearchpress.com by 34 "L.~~~poiso~iecl" system: react.io11 temperature -83O C…”

Section: The Reaction With Ammoniamentioning

confidence: 99%

The Rate of Reaction of Active Nitrogen With Ammonia and Ethylene

Wright¹,

Winkler²

1962

Can. J. Chem.

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The rate coristants for the reactions of C?Hr and NH3 are determined by termination of the reactions ill the gas phase after different times of reaction. The average value for the rate constant of the S atom -C2H4 reaction a t 150° C is 1.8X10'0 cc i n~l e -~s e c -~, when the initial N-atom concentration is determined from the rnaxilnum production of HCN. The average value for the rate constant for the over-all reactio~i of S H 3 with excited nitrogen molecules, a t 104" C in the "poisoned" system, and 83" C in the "~rnpoisoned" system, for low initial flow rates of S H 3 , or short reaction time, is 2.2X1010 cc m~l e -~s e c -~. The decrease in value ~f this rate constant a t higher initial flow rates of X H ? and longer reaction times in the poisoned" system indicates that the species responsible for NI-I3 decomposition is generated during the decay of S atoms in the presence of NH3. The value for the NH3 reaction is disc~~ssed in terms of energy transfer.

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Sensitized phosphorescence in organic solutions at low temperature. Energy transfer between triplet states

Cited by 202 publications

References 0 publications

Fast transient absorption spectroscopy of the early events in photoexcited chiral benzophenone–naphthalene dyads

Fast transient absorption spectroscopy of the early events in photoexcited chiral benzophenone–naphthalene dyads

A theory ofnonverticaltriplet energy transfer in terms of accurate potential energy surfaces: The transfer reaction from π,π* triplet donors to 1,3,5,7-cyclooctatetraene

The Rate of Reaction of Active Nitrogen With Ammonia and Ethylene

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