The photochemistry of 2-furaldehyde vapour. I. Photophysical processes: phosphorescence excited in the π* ← n transition

1976 ◽  
Vol 54 (19) ◽  
pp. 3089-3094 ◽  
Author(s):  
A. Gandini ◽  
P. A. Hackett ◽  
R. A. Back
Keyword(s):  
Quantum Yield ◽  
Pressure Dependence ◽  
Intersystem Crossing ◽  
Absorption Bands ◽  
Excited Triplet ◽  
Photophysical Processes

A search was made for emission from 2-furaldehyde, following excitation in the first two absorption bands. Only phosphorescence from the 3nπ* state was observed. The pressure dependence of the lifetime and quantum yield of this emission was determined, as well as that of the quantum yield of intersystem crossing. A mechanism involving self-quenching of excited triplet 2-furaldehyde is proposed.

Photocyanation of 3,4-dimethoxy-1-nitrobenzene. A quantitative study

1986 ◽  
Vol 51 (2) ◽  
pp. 358-367 ◽  
Author(s):  
Petr Kuzmič ◽  
Milan Souček
Keyword(s):  
Quantum Yield ◽  
Quantitative Study ◽  
Rate Constant ◽  
Potassium Cyanide ◽  
Intersystem Crossing ◽  
Excited Triplet ◽  
Cyanide Anion ◽  
Tert Butanol ◽  
Diffusion Controlled ◽  
Triplet Lifetime

UV photolysis (365 nm) of 3,4-dimethoxy-1-nitrobenzene in the presence of potassium cyanide leading to 3-cyano-4-methoxy-1-nitrobenzene was subjected to a quantitative photokinetic study. The reaction exhibits a second order kinetics with respect to the nucleophile and is effectively quenched by molecular oxygen as well as 2,4-hexadienoic acid. The excited triplet lifetime of 0.9 microseconds was determined on the basis of the dependence of quantum yield on the nucleophile and quencher concentrations in 50% aqueous tert-butanol. The quantum yield of intersystem crossing is at least 0.38 in the same solvent; bimolecular rate constant for the interaction of triplet 3,4-dimethoxy-1-nitrobenzene with cyanide anion has the value of 5.6 . 108 l . mol-1s-1, which is approximately one half of the rate constant for diffusion controlled quenching. Quantum yield of the reaction is strongly dependent on the water content in mixtures with tert-butanol and increases from 0.04 in water to 0.68 in 88% tert-butanol.

Photolysis of ketene. I

1968 ◽  
Vol 46 (14) ◽  
pp. 2353-2360 ◽  
Author(s):  
A. N. Strachan ◽  
D. E. Thornton
Keyword(s):  
Carbon Monoxide ◽  
Quantum Yield ◽  
Triplet State ◽  
Singlet State ◽  
Inert Gases ◽  
Inert Gas ◽  
Excited Singlet State ◽  
Intersystem Crossing ◽  
Excited Singlet ◽  
Increasing Temperature

Ketene has been photolyzed at 3660 and 3130 Å both alone and in the presence of the inert gases C4F8 and SF6. The quantum yield of carbon monoxide has been determined at both wavelengths as a function of pressure and temperature. At 3660 Å the quantum yield decreases with increasing pressure but increases with increasing temperature. At 3130 Å the quantum yield with ketene alone remains 2.0 at both 37 and 100 °C at pressures up to 250 mm. At higher pressures of ketene or with added inert gas the quantum yield decreases with increasing pressure. The results are interpreted in terms of a mechanism in which intersystem crossing from the excited singlet state to the triplet state occurs at both wavelengths, and collisional deactivation of the excited singlet state by ketene is single stage at 3660 Å but multistage at 3130 Å.

Effects of Pressure and Temperature on the Fluorescence Quantum Yield of N-Methylacridone in Solution Interpreted in Terms of the Eyring Transition-StateTheory

1981 ◽  
Vol 36 (5) ◽  
pp. 489-493
Author(s):  
H.-D. Brauer ◽  
R. Schmidt ◽  
B. Hammerich
Keyword(s):  
Quantum Yield ◽  
Fluorescence Quantum Yield ◽  
Energy Gap ◽  
State Theory ◽  
Intersystem Crossing ◽  
Thermally Activated ◽  
Elevated Pressures ◽  
Condon Factors ◽  
Positive Volume ◽  
Franck Condon

Abstract The influence of temperatur and pressure on the fluorescence quantum yield of N-methylacridone (9,10-dihydro-9-oxo-10-methyl-acridine) in toluene in the range of 283-313 K and 1 bar to 2.5 kbar, respectively, has been investigated. Treatment of the data in terms of the Eyring transition-state theory leads to a consistent interpretation of the observed effect. The unusually large increase of the quantum yield with increasing pressure is attributed to a positive volume of activation, ⊿V≠, for the thermally activated S1-T2 intersystem crossing which is known to be the only deactivation process (of the Si-state) competing with fluorescence. Comparison of the values for ⊿H≠, the activation enthalpy of this process, determined at various pressures, indicates a decrease in ⊿H≠ at elevated pressures. Since ⊿H≠ can be associated with the S1-T2 energy gap involved in intersystem crossing, this result further confirms the conclusion that the change in Franck-Condon factors alone cannot account for the decrease in the intersystem crossing rate with increasing pressure.

Identification of a receiver triplet state in the ultrafast intersystem crossing of carbonylpyrenes

2020 ◽  
Vol 22 (11) ◽  
pp. 6145-6153
Author(s):  
Lekshmi R. S. ◽  
Gayathri B. Kurup ◽  
Sivaranjana Reddy Vennapusa
Keyword(s):  
Quantum Yield ◽  
Triplet State ◽  
Intersystem Crossing

The intersystem crossing receiver triplet state lifetime dictates the efficiency of the triplet quantum yield in carbonylpyrenes.

The Photolysis in Acidic Aqueous Solutions of the Monooxalato-bisethylenediamine Chromium(III) Cation and the Bisoxalatomonoethylenediamine Chromate(III) Anion: Photolysis Modes and Quantum Yields

1971 ◽  
Vol 49 (3) ◽  
pp. 375-383 ◽  
Author(s):  
A. D. Kirk ◽  
K. C. Moss ◽  
J. G. Valentin
Keyword(s):  
Quantum Yield ◽  
Aqueous Solutions ◽  
Quantum Yields ◽  
Ligand Field ◽  
Intersystem Crossing ◽  
Empirical Correlations ◽  
Complex Ions ◽  
Ethylenediamine Complex ◽  
Ethylenediamine Ligand ◽  
Ph Range

The photolysis reactions of the complex ions [Cr(en)2ox]+ and [Cren(ox)2]− have been studied in the pH range 1 → 3 and at temperatures from 0 to 25 °C. It has been found that both ions photoaquate to a monodentate protonated ethylenediamine complex which then undergoes further aquation thermally with loss of the ethylenediamine ligand. Quantum yields for these aquations were measured for irradiation into the ligand field bands, the values obtained being 0.18 and 0.02, respectively. The results are discussed in terms of known empirical correlations for Cr(III) complexes. Assuming these reactions may occur from the 4T2g state as precursor, arguments are presented that the correlation between quantum yield and ΔE may depend on mixing of the 4T2g and 2Eg states, and its effect on the intersystem crossing rate constant.

The radiation-induced formation of excited states of aromatic hydrocarbons in alicyclic hydrocarbons I. Yields of excited singlet and triplet state solute molecules

1975 ◽  
Vol 347 (1648) ◽  
pp. 61-73 ◽  
Keyword(s):  
Energy Transfer ◽  
Excited States ◽  
Pulse Radiolysis ◽  
Minor Role ◽  
Intersystem Crossing ◽  
Excited Singlet ◽  
Excited Triplet ◽  
Upper Limit ◽  
Radiation Induced ◽  
A Minor

The dependences on concentration of the yield of excited triplet naphthalene, G ( 3 Naph٭), and of the radiation-induced fluorescence obtained on pulse radiolysis of solutions of naphthalene in cyclopentane, cyclooctane and decalin are reported. The yields of singlet excited naphthalene, G( 1 Naph٭), formed on pulse radiolysis of these solutions have been determined by comparing the intensity of the radiation-induced fluorescence with that obtained on photo excitation and the extent of formation of 3 Naph٭ by intersystem crossing, G ( 3 Naph٭) i. s. c., is assessed. Upper limit yields of solvent excited states, G ( 1 RH٭), were determined by measuring the extent of singlet energy transfer to toluene. It is concluded that energy transfer from solvent excited states plays a minor role in the formation of excited states of aromatic solutes.

Quantum yield for intersystem crossing in nonfluorescent metal porphyrins

1973 ◽  
Vol 18 (4) ◽  
pp. 543-545 ◽  
Author(s):  
K. N. Solov'ev ◽  
M. P. Tsvirko ◽  
V. V. Sapunov
Keyword(s):  
Quantum Yield ◽  
Intersystem Crossing ◽  
Metal Porphyrins

Spectrofluorometric studies. VIII. The effect of CO2 and CHCl3 on the photochemistry of monofluorobenzene

1970 ◽  
Vol 48 (10) ◽  
pp. 1607-1613 ◽  
Author(s):  
M. E. MacBeath ◽  
I. Unger
Keyword(s):  
Quantum Yield ◽  
Quantum Yields ◽  
Vibrationally Excited ◽  
Excited Triplet ◽  
Improved Technique ◽  
Triplet Quantum Yields

The sensitized emission of biacetyl technique was used to study the effect of CHCl3 and CO2 on the triplet quantum yields of both benzene and monofluorobenzene.The monofluorobenzene was studied at λ excitation (λex) of 2470, 2590, and 2670 Å. At 2470 Å, the triplet yield increased by over 40% with both added gases; at λex 2590 Å, by around 30%; and at λex 2670 Å, about 20%. CHCl3 is slightly more effective than CO2 in enhancing the biacetyl phosphorescent yield. The quantum yield of fluorescence was unchanged with these added gases. Using a slightly improved technique, the comparison irradiation of a benzene–biacetyl mixture at λex 2540 Å with added CHCl3 was repeated. The results confirmed that the biacetyl phosphorescent yield decreased with increasing pressures of CHCl3, but suggest that the effect is not as great as previously reported. At the same wavelength, the triplet yield is unaffected by the addition of CO2. The quantum yield of fluorescence of benzene is virtually unaffected by the added gases. The data suggest that in the monofluorobenzene case the CO2 and CHCl3 are quenching vibrationally excited triplet fluorobenzene molecules.

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