The effect of wavelength on organic photoreactions in solution.  Reactions from upper excited states

Turro, Nicholas J.; Ramamurthy, V.; Cherry, W. R.; Farneth, W. E.

doi:10.1021/cr60312a003

Cited by 252 publications

(141 citation statements)

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“…27 However, in the case of aryl halides involving the electronic system of the aromatic ring, the early experimental results have shown that predissociation seems dominant over direct dissociation and the dissociation is suggested to complete on a picosecond time scale. [28][29][30] For example, Freedman et al 10 reported that the photodecomposition of C 6 H 5 Cl at 193 nm occurred from the first excited singlet state (S 1 ) which was internally converted from the third excited singlet state (S 3 ). Dzvonik et al 8 measured the angular distribution of iodine atom in iodobenzene photodissociation and pointed out that the dissociation was indirect and the dissociative lifetime was about 0.5 ps.…”

Section: Introductionmentioning

confidence: 99%

Photodissociation of bromobenzene at 266 nm

Zhang

Zhu

Wang

et al. 1999

The Journal of Chemical Physics

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The photodissociation of C 6 H 5 Br at 266 nm has been investigated on the universal crossed molecular beam machine, and time-of-flight spectra as well as the angular distribution of Br atom have been measured. Photofragment translational energy distribution P(E t ) reveals that about 47% of the available energy is partitioned into translational energy. The anisotropy parameter ␤ at this wavelength is Ϫ0.7Ϯ0.2. From P(E t ) and ␤, we deduce that C 6 H 5 Br photodissociation is a fast process and the transition dipole moment is almost perpendicular to the C-Br bond. Ab initio calculations have been performed, and the calculated results show that the geometry of the first excited state of bromobenzene has changed apparently compared with that of the ground state. Two kinds of possible fast dissociation mechanism have also been proposed.

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Section: Introductionmentioning

confidence: 99%

Photodissociation of bromobenzene at 266 nm

Zhang

Zhu

Wang

et al. 1999

The Journal of Chemical Physics

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“…) with k IC = 7x10 8 s À1 ; [28] however, this is not the case with ttbP9, for which the gap as small as 3900 cm Based on the aforementioned, the first singlet state in the Jablonski diagram for ttbP9 must be 1 1 B u , which can be directly reached by absorption of light, so the emission must also correspond to the transition 1 1 B u !1 1 A g and the compound obeys Kashas rule. This, however, does not exclude the potential generation of other molecular structures of ttbP9 from the 1 1 B u state; however, it is rather inconsistent with the presence of an excited electronic state only 3900 cm À1 below 1 1 B u and usurping the assignation of the S 1 state in the Jablonski diagram for the photophysical processes of ttbP9.…”

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confidence: 99%

Electronic Energy Levels in all‐trans Long Linear Polyenes: The Case of the 3,20‐Di(tert‐butyl)‐2,2,21,21‐tetramethyl‐all‐trans‐3,5,7,9,11,13,15,17,19‐docosanonaen (ttbp9) Conforming to Kasha's Rule

Catalán

Hopf

Mlynek

et al. 2005

Chemistry A European J

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The absorption, fluorescence and fluorescence excitation spectra for 3,20-di(tert-butyl)-2,2,21,21-tetramethyl-all-trans-3,5,7,9,11,13,15,17,19-docosanonaen (ttbP9) in dilute solutions of 2-methylbutane were recorded at temperatures over the range 120-280 K. The high photostability of this nonaene allows us to assert that it exhibits a single fluorescence and that this can be unequivocally assigned to emission from its 1(1)B(u) excited state, it being the first excited electronic state. Available photophysical data for this polyene and the wealth of information reported for shorter all-trans polyenes allow us to conclude that if the first excited electronic state for the chromophore possessed 2(1)A(g) symmetry, then the energy of such a state might have been so close to that of the 1(1)B(u) state that: 1) the radiationless internal conversion mechanism would preclude the observation of the emission from the 1(1)B(u) state reported in this work and 2) the 2(1)A(g) state reached through internal conversion would be vibrationally coupled to 1(1)B(u) and would facilitate the detection of the emission from 2(1)A(g), which was not observed in any of the solvents used in this work. The spectroscopic and photochemical implications of these findings for other polyenes are discussed.

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“…Since that time several examples of reactions of this type have been studied. 20 The holographic technique Is particularly useful for studying such processes because it can be used even In cases where an interfering reaction occurs from the lowest triplet state. 4 To illustrate the use of holography in this case, we will consider the phoodsoclation of carbazole.…”

Section: Rbudge From H Wr Excited Tplet Statesmentioning

confidence: 99%

Applications of Holography in the Investigations of Photochemical Reactions.

Burland¹

1982

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The effect of wavelength on organic photoreactions in solution. Reactions from upper excited states

Cited by 252 publications

References 46 publications

Photodissociation of bromobenzene at 266 nm

Photodissociation of bromobenzene at 266 nm

Electronic Energy Levels in all‐trans Long Linear Polyenes: The Case of the 3,20‐Di(tert‐butyl)‐2,2,21,21‐tetramethyl‐all‐trans‐3,5,7,9,11,13,15,17,19‐docosanonaen (ttbp9) Conforming to Kasha's Rule

Applications of Holography in the Investigations of Photochemical Reactions.

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