S
 0↔S1 transition of trans-β-methyl styrene: Vibronic structure and dynamics

Haas, Yehuda; Kendler, Shai; Zingher, E.; Zuckermann, H.; Zilberg, Shmuel

doi:10.1063/1.469606

Cited by 23 publications

(25 citation statements)

References 25 publications

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“…[3][4][5] It was found that the method is useful for this purpose, as judged by comparison with experimental results. Practical considerations limited the size of the basis set that could be used in these calculations.…”

Section: Introductionmentioning

confidence: 96%

Ab Initio Study of the Low-Lying Electronic States of Indene

1996

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An ab initio calculation of the properties of the ground state and some low-lying electronic states of indene is reported. The results are compared with experimental data obtained by infrared and Raman spectroscopy, and with a recent fluorescence and resonance enhanced multiphoton ionization spectra obtained in a supersonic jet. The results show that the configuration interaction singles method can be used as a good approximation to calculate the molecular frequencies of the electronically excited states. It is found that as in other small aromatic molecules, the frequencies of out-of-plane modes tend to decrease, while those of in-plane ones are not changed significantly, except for a Kekulé type vibration, that shows a dramatic increase in the S 1 state. In contrast with the S 1 state, which is found to be bound, the S 2 state is reactive. This is compatible with the diffuse absorption spectrum and the photochemical activity of this state. These results are compared with a similar recent study of styrene.

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Section: Introductionmentioning

confidence: 96%

Ab Initio Study of the Low-Lying Electronic States of Indene

1996

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“…[10][11][12] Phosphorescence has never been detected from photoexcited styrene; however, many studies have suggested that photochemical cis-trans isomerisation mechanisms for styrene proceed via triplet states. 11,[13][14][15] known to have a nanosecond timescale. The only ultrafast decay pathway from S 1 is to S 0 directly via a conical intersection, requiring extra vibrational energy.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast dynamics through conical intersections and intramolecular vibrational energy redistribution in styrene

Nunn

Minns

Spesyvtsev

et al. 2010

Phys. Chem. Chem. Phys.

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We report a femtosecond time-resolved photoelectron spectroscopy (TRPES) investigation of internal conversion in the first two excited singlet electronic states of styrene. We find that radiationless decay through an S 1 /S 0 conical intersection occurs on a timescale of ~4 ps following direct excitation to S 1 with 0.6 eV excess energy, but that the same process is significantly slower (~20 ps) if it follows internal conversion from S 2 to S 1 after excitation to S 2 with 0.3 eV excess energy (0.9 eV excess energy in S 1 ).

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“…The latter molecule was studied in order to assign the jet cooled fluorescence excitation and emission spectra reported in the companion paper. 15 The structures of these molecules and the atom numbering convention are shown in Fig. 1.…”

Section: Introductionmentioning

confidence: 99%

“…14,15 The low lying electronic states of styrene, which is the simplest molecule containing both an aromatic ring and a double bond, have been extensively studied experimentally 16 -20 and theoretically. [21][22][23][24][25] Experimental data based primarily on UV spectroscopy indicate that the molecule is planar in both the ground and the first electronically excited singlet states.…”

Section: Introductionmentioning

confidence: 99%

Ab initio study of styrene and β-methyl styrene in the ground and in the two lowest excited singlet states

Zilberg

Haas

1995

The Journal of Chemical Physics

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The structure and vibrational frequencies of styrene and trans-β-methyl styrene in the lowest three singlet states (S0, S1, and S2) have been calculated using ab initio quantum chemical methods. The frequencies are compared with experimental data obtained in the bulk and in a supersonic jet. The calculation shows that in the ground state the molecules have a broad shallow potential as a function of the torsional angle, are essentially planar, but may be slightly bent. In the S1 and S2 states, the molecules are planar; In S1, the main structural change is in the aromatic ring, that is somewhat expanded. In S2, the C=C vinyl double bond elongates, while the C1—Cα single bond becomes shorter, bringing these two bonds to almost equal length. Correlation diagrams connecting ground state vibrational modes with ones belonging to electronically excited states are given; they show that for many out-of-plane modes the vibrational frequencies decrease upon electronic excitation. This is accounted for in terms of the changes in the π electron distribution taking place upon optical excitation that result in decreasing the force constants characterizing these vibrations. The frequencies of most in-plane modes change very little, but mixing between S0 modes is indicated in some cases, and a few vibrations, among them a Kekulé-type mode, undergo considerable change. The relation to the spectroscopy of the corresponding transitions in benzene is briefly discussed.

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S 0↔S1 transition of trans-β-methyl styrene: Vibronic structure and dynamics

Cited by 23 publications

References 25 publications

Ab Initio Study of the Low-Lying Electronic States of Indene

Ab Initio Study of the Low-Lying Electronic States of Indene

Ultrafast dynamics through conical intersections and intramolecular vibrational energy redistribution in styrene

Ab initio study of styrene and β-methyl styrene in the ground and in the two lowest excited singlet states

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