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Vibrations of porphycene in the S0 and S1 electronic states: Single vibronic level dispersed fluorescence study in a supersonic jet
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Image of Scheme 1.
Scheme 1.

Structural formulas of porphycene (a) and porphyrin (b).

Image of FIG. 1.
FIG. 1.

LIF excitation spectrum of porphycene in the range up to 1400 cm excess energy above the origin of the S-S electronic transition.

Image of FIG. 2.
FIG. 2.

Active baseline subtraction spectrum (top, blue) of porphycene obtained while pumping the band of the LIF excitation spectrum. The scanning probe laser was delayed by 200 ns with respect to the fixed pump laser. (Bottom) The spectra obtained with and without pumping (black and red, respectively).

Image of FIG. 3.
FIG. 3.

Comparison of LIF excitation (black, top) and dispersed fluorescence (red, bottom) spectra of porphycene in supersonic jet. Fluorescence intensity in the dispersed fluorescence spectrum is multiplied by −1 for easier comparison.

Image of FIG. 4.
FIG. 4.

Dispersed fluorescence spectrum of porphycene recorded for excitation into the origin band (16 163 cm). Frequencies are given in wavenumbers relative to the excitation energy.

Image of FIG. 5.
FIG. 5.

Comparison of dispersed fluorescence spectra obtained for selective excitation into both components of tunneling doublets: (a) and , (b) 107/112, (c) 136/141, (d) 150/155 cm.

Image of FIG. 6.
FIG. 6.

Dispersed fluorescence spectra obtained for excitation into low-frequency bands: (a) 144 cm, (b) 174 cm, (c) 220 cm, (d) 398 cm.

Image of FIG. 7.
FIG. 7.

Dispersed fluorescence spectrum obtained via excitation of (a) 0+ 184, (b) 0+362, (c) 0+364, and (d) 0 + 541 cm bands.

Image of FIG. 8.
FIG. 8.

Dispersed fluorescence spectrum obtained for excitation into (a) 0 + 339, (b) 0 + 364, (c) 0 + 400, (d) 0 + 481, and (e) 0 + 519 cm bands.

Image of FIG. 9.
FIG. 9.

Dispersed fluorescence spectra obtained via excitation of (a) 0 + 826 cm, (b) 0 + 909 cm, and (c) 0 + 951 cm bands.

Image of FIG. 10.
FIG. 10.

Comparison of experimental and calculated vibrational modes of porphycene in the ground (bottom) and the lowest excited singlet state (top). A and C, B3LYP/6-31G(d,p), B and D, B3LYP/6-311++G(d,p) calculations. The plots for S include also the 8A mode at 810 cm, not observed in the present work.

Image of FIG. 11.
FIG. 11.

Displacement vectors of 1A, 2A, 1B, and 2B normal modes, obtained using B3LYP/6-311++G(d,p) calculations.


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Table I.

Ground and excited state (S) vibrational frequencies of porphycene obtained from LIF and SVL fluorescence spectra.

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Table II.

Comparison of experimental and calculated low frequency modes of porphycene in S and S electronic states. The calculated values include scaling factors (see text).

Generic image for table
Table III.

Ground state tunneling splitting of the 2A mode obtained from SVL spectra for different vibrationally excited levels.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Vibrations of porphycene in the S0 and S1 electronic states: Single vibronic level dispersed fluorescence study in a supersonic jet