Picosecond time-resolved fluorescence spectroscopy of molecular vapors

Moore, Robert K.; Doany, F. E.; Heilweil, Edwin J.; Hochstrasser, Robin M.

doi:10.1021/j150649a011

Cited by 12 publications

(1 citation statement)

References 3 publications

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“…In particular, we find that off-resonance cubic anharmonic coupling to states other than the light state is responsible for the addition of the majority of states to the strong matrix. The coupled states thus tend to span a wide energy range (>100 cm"1 for fc(3) = 20 cm"1), and only a few of the resulting eigenstates lie within the energy width of a picosecond source. While our calculations suggest that the higher order anharmonic coupling terms do not cause significant mixing of pairs of states, these terms certainly add to the total unstructured emission by virtue of the large number of states that couple through such terms.…”

Section: General Trends From P -Difluorobenzene Calculationsmentioning

confidence: 99%

Calculations of vibrational state mixing leading to intramolecular vibrational energy redistribution in the onset region: application to S1 p-difluorobenzene

Whetton¹,

Lawrance²

1989

J. Phys. Chem.

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mol"1 for the energy barrier for the movement of the beryllium atom between the positions Be and Be' in the solid state has been reported.22 This barrier is so high that the rate of movement of the beryllium atom would be negligible. The barrier must, however, be significantly larger than 5 kJ mol"1, as the rearrangements of the C-C bonds of the rings required as a part of this motion would be expected to require a reasonable amount of energy.For this reason it appears likely that the movement of the beryllium atom between the two sites is a tunnelling phenomenom and that the activation energy observed corresponds to the rearrangement of the solvent molecules as the dipole of the molecule is reversed. This effect is likely to be more important in diethyl ether, which is polar, than in cyclohexane. If the activation energy observed is assumed to be due to the solvent reorganization, the barrier for cyclohexane solution would be expected to be very low, while that for diethyl ether solution would be close to the activation (22) Marynick, D.

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Section: General Trends From P -Difluorobenzene Calculationsmentioning

confidence: 99%