Vibronic Structure in the Fluorescence Lifetimes and Quantum Yields of Aniline Vapor

Weyssenhoff, Hanns von; Kraus, F.

doi:10.1063/1.1675192

Cited by 51 publications

(9 citation statements)

References 19 publications

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“…The low value of the effective frequency may be due to the change in geometry of the amino group. von Weyssenhoff & Kraus (93) found structure in the rate for intersystems crossing from Sl in aniline, which they also relate to the umbrella mode of the amino group.…”

Section: F Lifetime Of Single Vmronic Levelsmentioning

confidence: 95%

“…Aniline appears to be another example for which both lifetime and quantum yield data is available, in this case from the same laboratory (93). The structure in the spectra again points to a noncommunicating system.…”

Section: Nanosecond Flash Spectroscopymentioning

confidence: 95%

“…This is unfortunately not an abso lute method, and has the further disadvantage that in its simplest arrangement (293) it assumes that the spectral response of photomultipliers is uniform. More sophisticated measurements have now been performed (93), however, using a fluorescing screen which has a uniform spectral response and produces a spectrally even photo detector. Still, the measurements are only relative to the value of a thermalized distribution.…”

Section: Nanosecond Flash Spectroscopymentioning

confidence: 99%

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Lifetimes in Excited States

Schlag¹,

Schneider²,

Fischer³

1971

Annu. Rev. Phys. Chem.

180

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Section: F Lifetime Of Single Vmronic Levelsmentioning

confidence: 95%

Section: Nanosecond Flash Spectroscopymentioning

confidence: 95%

Section: Nanosecond Flash Spectroscopymentioning

confidence: 99%

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Lifetimes in Excited States

Schlag¹,

Schneider²,

Fischer³

1971

Annu. Rev. Phys. Chem.

180

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“…The vibronic and spin-orbit selection rules on the matrix elements Jk(m, n) have been applied in the analysis of a variety of data for organic molecules [1, 5,35]. Similar symmetry based arguments have been used by Gardner and Kasha [36] in their definition of ' vibrationally deficient' molecules, i.e.…”

Section: The Electronic Factor Jk(m N)mentioning

confidence: 99%

Radiationless processes in transition-metal complexes

Robbins¹,

Thomson

1973

Molecular Physics

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This work applies recent theories of radiationless relaxation processes to the case of transition-metal complexes. Existing theories developed for understanding radiationless transitions in organic molecules separate coupling terms into electronic and vibrational factors. In this work the symmetry based selection rules on the coupling terms are examined since the high symmetry of many transition-metal complexes offers the possibility that strict selection rules will operate. First, the theoretical expressions have been extended to include the spin-orbit coupling operator in the zeroth order hamiltonian. This then allows application of the final expressions to transition metal ions of any atomic number and also permits derivation of selection rules for relaxation processes between spinor states. Secondly, the application of the vibrational factor, which is a product of a promoting term and an overlap factor or accepting term, to a series of octahedral and pseudooctahedral Cr(I I I) complexes, studied by Forster and co-workers, is described. It is shown that there is a good linear correlation between the radiationless transition rate ~Er and the number of active hydrogen atoms on the ligands. It is concluded that the highest frequency internal ligand modes are acting as promoting modes. This can be understood by examination of the selection rules on the electronic factors which show that, for the 2Eg~4A~g process in Cr(III), there are no vibrations of the metal-ligand framework likely to be efficient as promoting modes. Finally, the selection rules are given for the electronic coupling factors between the lowest excited and ground states of all the d configurations of both tetrahedral and octahedral complexes of the first row of transition metal ions. A comparison of these rules with available experimental data shows there is some correlation between the occurrence of emission and the absence of a promoting mode among the skeletal vibrations of the complex considered.

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“…Aniline has often been used as a model system because of conveniently located electronic transitions, [27][28][29] an interesting intersystem crossing ͑ISC͒, 30,31 and because, while being a relatively small molecule with a well-understood vibrational structure, aniline exhibits many characteristics of large molecules. The geometry and the vibrational structure of the ground electronic state ͑ 1 A I ͒ ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

Time-delayed two-color photoelectron spectra of aniline, 2-aminopyridine, and 3-aminopyridine: Snapshots of the nonadiabatic curve crossings

Kim

Schick

Weber

1995

The Journal of Chemical Physics

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Articles you may be interested inTwo-color pump-probe laser spectroscopy instrument with picosecond time-resolved electronic delay and extended scan range Rev. Sci. Instrum. 76, 114301 (2005); 10.1063/1.2126808 Vibrational spectra of aniline-Ar n van der Waals cations (n=1 and 2) observed by twocolor ''threshold photoelectron'' [zero kinetic energy (ZEKE)photoelectron] spectroscopy J. Chem. Phys. 96, 6399 (1992); 10.1063/1.462634 Twocolor threshold photoionization of jetcooled aniline: Vibrationally selective autoionization J. Chem. Phys. 84, 6771 (1986); 10.1063/1.450680 Autoionizing Rydberg structure observed in the vibrationally selective, twocolor, threshold photoionization spectrum of jetcooled aniline J. Chem. Phys. 83, 4820 (1985); 10.1063/1.449010Timeresolved twocolor photoacoustic and multiphoton ionization spectroscopy of aniline

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Vibronic Structure in the Fluorescence Lifetimes and Quantum Yields of Aniline Vapor

Cited by 51 publications

References 19 publications

Lifetimes in Excited States

Lifetimes in Excited States

Radiationless processes in transition-metal complexes

Time-delayed two-color photoelectron spectra of aniline, 2-aminopyridine, and 3-aminopyridine: Snapshots of the nonadiabatic curve crossings

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