Formation rate constant and features of the excited complexes upon concentration quenching of the triplet state of Pd-porphyrins in toluene

2000 ◽  
Vol 88 (3) ◽  
pp. 359-364 ◽  
Author(s):  
V. V. Sapunov
Keyword(s):  
Triplet State ◽  
Rate Constant ◽  
Formation Rate ◽  
Concentration Quenching ◽  
Excited Complexes

scholarly journals PROPERTIES OF EXCITED MOLECULES IN PHOTOLYSIS OF 2,6-DIPHENYL-1,4-BENZOQUINONE WITH AMINES

2018 ◽  
Vol 61 (8) ◽  
pp. 27
Author(s):  
Dmitriy N. Gurulev ◽  
Lyubov V. Palatkina ◽  
Anna S. Yudina ◽  
Vladimir I. Porkhun
Keyword(s):  
Hydrogen Atom ◽  
Triplet State ◽  
Rate Constant ◽  
Energy State ◽  
Photochemical Reactions ◽  
Science Literature ◽  
Initial Event ◽  
Donor Acceptor ◽  
High Reduction ◽  
Excited Complexes

To date, it is considered established that quinones with lower energy state, under the action of light tear away a hydrogen atom from a hydrocarbon or an electron donor from inorganic anion-radicals, which have a high reduction potential. However, even for the simplest quinones (1,4-benzoquinone, 1,4-naphthoquinones, 9,10-anthraquinone and their derivatives) there is no consensus in the science literature about the nature of the initial event in photoreaction with compounds which are potential donors of hydrogen atom and electron. The first step in many photochemical reactions is the formation of complexes between donors and acceptors of electrons in the excited state (exiplexes). Photoreactive quinones as elementary acts include the transfer of electron (or) hydrogen atom. The mechanism depends on the presence and strength of donor-acceptor complexes (DAC) of the quinones with the reagents. Studies of triplet exiplexes allow you to set the details of the elementary reaction acts. Only short-lived intermediate product was registered upon photoexcitation of the studied quinone Q in low-polarity solvents. The kinetic of decay of the first order with rate constant of about 2∙106 s-1 in toluene and dibutylphthalate and the introduction of oxygen leads to a decrease in the lifetime of the product in the triplet state. With the introduction of solutions of amines quenching of triplet state (QT) with rate constant close to diffusion was observed. Rate constants of quenching by dissolving in benzene and by dissolving in dibutyl phthalate were determined. It is established that formation of intermediate products is carried out from triplet state (QT). Excited complexes with charge transfer in acetonitrile were not observed. It is concluded that with decrease in electron affinity of the acceptors, when the connection of the molecules in the complex becomes weaker, the lifetime of TE increases significantly.

scholarly journals Triplet State Formation of Chromophoric Dissolved Organic Matter in Atmospheric Aerosols: Characteristics and Implications

2020 ◽  
Author(s):  
Qingcai Chen ◽  
Zhen Mu ◽  
Li Xu ◽  
Mamin Wang ◽  
Jin Wang ◽  
...  
Keyword(s):  
Organic Matter ◽  
Dissolved Organic Matter ◽  
Triplet State ◽  
Atmospheric Aerosols ◽  
Formation Rate ◽  
Chromophoric Dissolved Organic Matter ◽  
Biomass Combustion ◽  
Triplet States ◽  
Ambient Aerosols ◽  
Paramagnetic Resonance

Abstract. There is chromophore dissolved organic matter (CDOM) in the atmosphere, which may form triplet-state chromophoric dissolved organic matter (3CDOM*) to further driving the formation of reactive oxygen species (ROS) under solar illumination. 3CDOM* contributes significantly to aerosol photochemistry and plays an important role in aerosol aging. We quantify the ability to form 3CDOM* and drive the formation of ROS by primary, secondary and ambient aerosols. Biomass combustion has the strongest 3CDOM* generation capacity and the weakest vehicle emission capacity. Ambient aerosol has a stronger ability to generate 3CDOM* in winter than in summer. Most of the triplet states generation conform to first-order reaction, but some of them do not due to the different quenching mechanism. The structural-activity relationship between the CDOM type and the 3CDOM* formation capacity shows that the two types of CDOM identified, which similar to the nitrogen-containing chromophores contributed 88 % to the formation of 3CDOM*. The estimated formation rate of 3CDOM* can reach ~ 100 μmol m−3 h−1 in the atmosphere in Xi'an, China, which is approximately one hundred thousand-times the hydroxyl radical (•OH) production. This study verified that 3CDOM* drives at least 30 % of the singlet oxygen (1O2) and 31 % of the •OH formed by aerosols using the spin trapping and electron paramagnetic resonance technique.

Detection and chemistry of the triplet state of thymine

1970 ◽  
Vol 48 (4) ◽  
pp. 694-696 ◽  
Author(s):  
A. G. Szabo ◽  
W. D. Rlddell ◽  
R. W. Yip
Keyword(s):  
Excited State ◽  
Triplet State ◽  
Rate Constant ◽  
Triplet Excited State

The transient produced on flash excitation of degassed solutions of thymine in acetonitrile has been characterized as the triplet excited state of thymine. This triplet state has a lifetime of 14 ± 1 μs and the associated dimerization rate was found to be 5.3 ± 0.3 × 108 M−1 s−1. The triplet state of thymine could be quenched by 2,4-hexadien-1-ol with a rate constant of 8.1 ± 0.6 × 109 M−1 s−1.

Phenyl Substitution Effects on Triplet–Triplet Absorption Spectra: I. Study of 1,3,6,8-Tetraphenylpyrene

1975 ◽  
Vol 53 (21) ◽  
pp. 3269-3275 ◽  
Author(s):  
C. Rullière ◽  
E. C. Colson ◽  
P. C. Roberge
Keyword(s):  
Absorption Spectrum ◽  
Triplet State ◽  
Absorption Spectra ◽  
Rate Constant ◽  
Theoretical Calculations ◽  
Vibrational Structure ◽  
Substitution Effects ◽  
Quenching Rate ◽  
Diffusion Controlled ◽  
Quenching Rate Constant

The triplet–triplet (T–T) absorption spectrum of 1,3,6,8-tetraphenylpyrene (TPP) was measured from 400 to 620 nm. The data obtained are compared with theoretical calculations using the Ruedenberg–Scherr FEMO model. A planar triplet state is evidenced by fine vibrational structure. The T–T quenching rate constant measured (1.3 ± 0.1 × 109 M−1 s−1) is 20% of the expected diffusion-controlled value.

A reinvestigation of the interaction between triplet states of cyclohexenones and amines

1988 ◽  
Vol 66 (10) ◽  
pp. 2595-2600 ◽  
Author(s):  
D. Weir ◽  
J. C. Scaiano ◽  
D. I. Schuster
Keyword(s):  
Triplet State ◽  
Rate Constant ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Radical Cations ◽  
Laser Flash ◽  
Triplet States ◽  
New Evidence

Laser flash photolysis studies lead to the conclusion that the short-lived triplet states of cyclohexenones are readily quenched by amines. For example, in the case of 2-cyclohexen-1-one (1) its triplet state (τT = 40 ns in acetonitrile) is quenched by triethylamine with a rate constant of (9.0 ± 0.8) × 107 M−1 s−1. Cyclohexenone triplets are also quenched efficiently by DABCO and by triphenylamine leading to the formation of the corresponding amine radical cations. The new evidence reported rules out the involvement of long-lived detectable exciplexes.

Lifetime and quenching rate constant for the lowest triplet state of sulfur dioxide

1970 ◽  
Vol 92 (1) ◽  
pp. 217-218 ◽  
Author(s):  
Susan S. Collier ◽  
Akira. Morikawa ◽  
David H. Slater ◽  
Jack G. Calvert ◽  
George. Reinhardt ◽  
...  
Keyword(s):  
Sulfur Dioxide ◽  
Triplet State ◽  
Rate Constant ◽  
Quenching Rate ◽  
Quenching Rate Constant

Mechanism for triplet-state concentration quenching in xanthene dyes

1986 ◽  
Vol 44 (3) ◽  
pp. 232-235 ◽  
Author(s):  
K. T. Ermaganbetov ◽  
G. A. Ketsle ◽  
Z. M. Muldakhmetov ◽  
L. V. Chirkova
Keyword(s):  
Triplet State ◽  
Concentration Quenching ◽  
Xanthene Dyes ◽  
State Concentration
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