Low temperature laser fluorescence and excitation spectra of free base phthalocyanine in normal alkanes matrices (Shpolskii effect)

Hála, J.; Pelant, I.; Parma, L.; Vacek, K.

doi:10.1007/bf01596722

“…In the previous studies of phthalocyanine in solution, 7 isolated in organic solids 17,23 or matrices 5,6 the transition involving the vibrational mode around 1550 cm À1 is always either one of the more intense bands or the most intense band in emission spectra. The stimulated emission observed by Sorokin et al 7 for AlPc in ethanol was also on this vibronic transition.…”

Section: Discussionmentioning

confidence: 97%

Amplified emission of phthalocyanine isolated in cryogenic matrices

Dozova

¹

,

Murray

²

,

McCaffrey

³

et al. 2008

Phys. Chem. Chem. Phys.

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Laser induced fluorescence spectroscopy of free-base (H 2 Pc) and zinc (ZnPc) phthalocyanines trapped in rare gas and nitrogen matrices reveals a quite unexpected phenomenon with a moderate increase in the laser intensity. In all matrices except Xe, a huge increase occurs in the intensity of an emission band near 755 nm when pumping the S 1 ' S 0 transition. The band involves a vibrational mode of the ground state, located at 1550 and 1525 cm À1 for H 2 Pc and ZnPc, respectively. Many of the characteristics of amplified emission (AE) are exhibited by this vibronic transition. Excitation scans recorded for the AE band yield greatly enhanced site selectivity compared to what is obtained in normal fluorescence excitation scans.

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“…Thus the electronic spectroscopy of both molecules have been reported in the gas phase, 4,5 in low-temperature jets, [6][7][8] in He droplets 9,10 and in thin films. 11 The two molecules have also been studied in cryogenic matrices: either in Shpol'skii organic matrices [12][13][14] or isolated in the solid rare gases. [15][16][17][18] In a detailed magnetic circularly polarised luminescence (MCPL) study of ZnPc, Schatz and co-workers 19 identified the presence of both crystal field splitting and Jahn-Teller coupling on the degenerate first excited singlet state.…”

Section: Introductionmentioning

confidence: 99%

Visible luminescence spectroscopy of free-base and zinc phthalocyanines isolated in cryogenic matrices

Murray

¹

,

Dozova

²

,

McCaffrey

³

et al. 2011

Phys. Chem. Chem. Phys.

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The absorption, emission and excitation spectra of ZnPc and H 2 Pc trapped in Ne, N 2 , Ar, Kr and Xe matrices have been recorded in the region of the Q states. A comparison of the matrix fluorescence spectra with Raman spectra recorded in KBr pellets reveals very strong similarities. This is entirely consistent with the selection rules and points to the occurrence of only fundamental vibrational transitions in the emission spectra. Based on this behaviour, the vibronic modes in emission have been assigned using results obtained recently on the ground state with large basis-set DFT calculations [Murray et al. PCCP, 12, 10406 (2010)]. Furthermore, the very strong mirror symmetry between excitation and emission has allowed these assignments to be extended to the excitation (absorption) bands. While this approach works well for ZnPc, coupling between the band origin of the S 2 (Q Y ) state and vibrationally excited levels of S 1 (Q X ), limits the range of its application in H 2 Pc. The Q X /Q Y state coupling is analysed from data obtained from site-selective excitation spectra, revealing pronounced matrix and site effects. From this analysis, the splitting of the Q X and Q Y states has been determined more accurately than in any previous attempts.

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“…In the previous studies of phthalocyanine in solution, 7 isolated in organic solids 17,23 or matrices 5,6 the transition involving the vibrational mode around 1550 cm À1 is always either one of the more intense bands or the most intense band in emission spectra. The stimulated emission observed by Sorokin et al 7 for AlPc in ethanol was also on this vibronic transition.…”

Section: Discussionmentioning

confidence: 98%

A pair-potentials analysis of the emission spectroscopy of P13 state atomic mercury isolated in solid Ar, Kr, and Xe

Collier

¹

,

McCaffrey

²

2003

The Journal of Chemical Physics

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Laser induced fluorescence spectroscopy of free-base (H 2 Pc) and zinc (ZnPc) phthalocyanines trapped in rare gas and nitrogen matrices reveals a quite unexpected phenomenon with a moderate increase in the laser intensity. In all matrices except Xe, a huge increase occurs in the intensity of an emission band near 755 nm when pumping the S 1 ' S 0 transition. The band involves a vibrational mode of the ground state, located at 1550 and 1525 cm À1 for H 2 Pc and ZnPc, respectively. Many of the characteristics of amplified emission (AE) are exhibited by this vibronic transition. Excitation scans recorded for the AE band yield greatly enhanced site selectivity compared to what is obtained in normal fluorescence excitation scans.

show abstract

Low temperature laser fluorescence and excitation spectra of free base phthalocyanine in normal alkanes matrices (Shpolskii effect)

Cited by 7 publications

References 4 publications

Amplified emission of phthalocyanine isolated in cryogenic matrices

Amplified emission of phthalocyanine isolated in cryogenic matrices

Visible luminescence spectroscopy of free-base and zinc phthalocyanines isolated in cryogenic matrices

A pair-potentials analysis of the emission spectroscopy of P13 state atomic mercury isolated in solid Ar, Kr, and Xe

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