Mode- and complexation-specific singlet-triplet coupling in jet-cooled perylene studied by time-resolved fluorescence spectroscopy

Kaziska, Andrew J.; Wittmeyer, Stacey A.; Motyka, Andrea L.; Topp, Michael R.

doi:10.1016/0009-2614(89)87448-2

Cited by 18 publications

(10 citation statements)

References 24 publications

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“…We achieved the best agreement assuming a linewidth of 0.001 cm À1 , corresponds to a fluorescence lifetime of 5.3 ns. This is appreciably shorter than the observed lifetime by real-time measurement (8.88 ns) [9]. The discrepancy may be attributed to saturation broadening in the ultrahigh-resolution spectrum because this transition is very strong.…”

Section: Resultsmentioning

confidence: 66%

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Ultrahigh-resolution laser spectroscopy of the S1 1B2← S0 1A transition of perylene

Kowaka¹,

Suganuma²,

Ashizawa³

et al. 2010

Journal of Molecular Spectroscopy

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a b s t r a c tA rotationally resolved ultrahigh-resolution fluorescence excitation spectrum of the S 1 S 0 transition of perylene has been observed using a collimated supersonic jet technique in conjunction with a single-mode UV laser. We assigned 1568 rotational lines of the 0 0 0 band, and accurately determined the rotational constants. The obtained value of inertial defect was positive, accordingly, the perylene molecule is considered to be planar with D 2h symmetry. We determined the geometrical structure in the S 0 state by ab initio theoretical calculation at the RHF/6-311+G(d,p) level, which yielded rotational constant values approximately identical to those obtained experimentally. Zeeman broadening of each rotational line with the external magnetic field was negligibly small, and the mixing with the triplet state was shown to be very small. This evidence indicates that intersystem crossing (ISC) in the S 1 1 B 2u state is very slow. The rate of internal conversion (IC) is also inferred to be small because the fluorescence quantum yield is high. The rotational constants of the S 1 1 B 2u state were very similar to those of the S 0 1 A g state. The slow internal conversion (IC) at the S 1 zero-vibrational level is attributed to a small structural change upon electronic transition.

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Section: Resultsmentioning

confidence: 66%

“…The z-axis is out-of-plane. The fluorescence excitation spectrum and dispersed fluorescence spectra of the S 1 M S 0 transition of jet-cooled perylene have been already reported [7][8][9][10][11]. The 0 0 0 band is strongly observed at 401 nm.…”

Section: Resultsmentioning

confidence: 87%

Ultrahigh-resolution laser spectroscopy of the S1 1B2← S0 1A transition of perylene

Kowaka¹,

Suganuma²,

Ashizawa³

et al. 2010

Journal of Molecular Spectroscopy

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“…The short lifetime of a specific vibronic level has been similarly observed in the perylene molecule. 30 The S 1 1 B 3u state is coupled with the vibrational levels in the S 0 1 A g state by non-Born-Oppenheimer vibronic interaction. It might be supposed that the mixing with the S 0 state is closely related to the change in the geometrical molecular structure upon electronic excitation.…”

Section: Resultsmentioning

confidence: 99%

High-resolution spectroscopy of weak and short-lived bands of the S1 B13u←S A1g transition of naphthalene

Yoshida

Semba²,

Kasahara³

et al. 2009

The Journal of Chemical Physics

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Rotationally resolved high-resolution spectra and fluorescence decay curves have been observed for weak and short-lived vibronic bands of the S(1) (1)B(3u) <-- S(0) (1)A(g) transition of naphthalene. Fluorescence lifetime of the vibronic band with an excess energy of 1390 cm(-1) (0(0)(0) + 1390 cm(-1) band) is remarkably shorter than that of other bands. Zeeman splitting of rotational lines is very small, so that the main radiationless process is not intersystem crossing to the triplet state but internal conversion to the ground state. The lifetime is thought to be governed by the strength of vibronic coupling between vibrational levels of the S(0) and S(1) states. As for the 0(0)(0) + 2570 cm(-1) band, energy shifts were found in only a few rotational levels although the excess energy was higher than the threshold of intramolecular vibrational redistribution. We conclude that all of the rotational levels are mixed with other vibrational levels. The 0(0)(0) + 3068 cm(-1) band spectrum is fairly complicated with numerous rotational lines, which is attributed to strong vibronic coupling with the S(2) (1)B(2u) state.

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“…The observed fluorescence lifetimes of naphthalene ͑ϳ300 ns͒ and pyrene ͑ϳ1400 ns͒ are long in contrast to the short lifetimes of the S 1 1 B 2u states of anthracene ͑18 ns͒, tetracene ͑20 ns͒, 34 and perylene ͑8.9 ns͒. 35 It is noteworthy that the lifetime of pyrene is significantly longer than that of naphthalene in spite of the pyrene's larger molecular size and level density. The mixing with the S 2 1 B 2u state might be shortening the lifetime of the S 1 1 B 3u state.…”

Section: Excited-state Dynamics In the S 1 1 B 3u Statementioning

confidence: 88%

Vibrational and rotational structure and excited-state dynamics of pyrene

Baba

Saitoh

Kowaka

et al. 2009

The Journal of Chemical Physics

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Vibrational level structure in the S(0) (1)A(g) and S(1) (1)B(3u) states of pyrene was investigated through analysis of fluorescence excitation spectra and dispersed fluorescence spectra for single vibronic level excitation in a supersonic jet and through referring to the results of ab initio theoretical calculation. The vibrational energies are very similar in the both states. We found broad spectral feature in the dispersed fluorescence spectrum for single vibronic level excitation with an excess energy of 730 cm(-1). This indicates that intramolecular vibrational redistribution efficiently occurs at small amounts of excess energy in the S(1) (1)B(3u) state of pyrene. We have also observed a rotationally resolved ultrahigh-resolution spectrum of the 0(0) (0) band. Rotational constants have been determined and it has been shown that the pyrene molecule is planar in both the S(0) and S(1) states, and that its geometrical structure does not change significantly upon electronic excitation. Broadening of rotational lines with the magnetic field by the Zeeman splitting of M(J) levels was very small, indicating that intersystem crossing to the triplet state is minimal. The long fluorescence lifetime indicates that internal conversion to the S(0) state is also slow. We conclude that the similarity of pyrene's molecular structure and potential energy curve in its S(0) and S(1) states is the main cause of the slow radiationless transitions.

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Mode- and complexation-specific singlet-triplet coupling in jet-cooled perylene studied by time-resolved fluorescence spectroscopy

Cited by 18 publications

References 24 publications

Ultrahigh-resolution laser spectroscopy of the S1 1B2← S0 1A transition of perylene

Ultrahigh-resolution laser spectroscopy of the S1 1B2← S0 1A transition of perylene

High-resolution spectroscopy of weak and short-lived bands of the S1 B13u←S A1g transition of naphthalene

Vibrational and rotational structure and excited-state dynamics of pyrene

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