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Luminescence spectroscopy of matrix-isolated atomic manganese: Excitation of the “forbidden” transitions
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10.1063/1.1961531
/content/aip/journal/jcp/123/4/10.1063/1.1961531
http://aip.metastore.ingenta.com/content/aip/journal/jcp/123/4/10.1063/1.1961531

Figures

Image of FIG. 1.
FIG. 1.

An energy level diagram for gas phase atomic manganese showing the states that exist at energies lower than the state reached by a fully allowed electric-dipole transition from the ground state. The transition to the state as well as the forbidden and transitions, indicated by the arrows, occur at , and , respectively (Ref. 3). The gas phase radiative lifetimes (Refs. 4–6) for these transitions are also indicated, revealing the very large difference between the electric-dipole allowed transition and the forbidden transition.

Image of FIG. 2.
FIG. 2.

Laser excitation spectra recorded at in a sample annealed to , in the vicinity of the gas phase transition (dashed vertical line on the left) monitoring the blue and red site emission features present at 626 and , respectively. A comparison of the emission produced with red site excitation at is made on the right, with that produced with blue site excitation at . The excitation spectra shown on the extreme left were both recorded with Rhodamine 590, the scan shown in the middle trace in the upper panel was recorded with Rhodamine 610.

Image of FIG. 3.
FIG. 3.

High resolution laser excitation spectra recorded at in an annealed sample. The spectra were recorded with Rhodamine 590 monitoring emission at and with Rhodamine 610 monitoring emission and . The dashed vertical lines indicate the positions of the five gas phase (Ref. 3) transitions to the excited spin-orbit levels of the state. The emission spectrum shown on the right was recorded with excitation of the spin-orbit level at . It is evident that all features including the emission, are slightly blue of the gas phase transitions (Ref. 3), indicating a small matrix shift on the transitions. Particularly noteworthy is the overlap of the excitation and emission scans at recorded for the level.

Image of FIG. 4.
FIG. 4.

High-resolution scans of the emission produced with laser excitation at 578 and corresponding to the and transitions, respectively. Once the laser scatter (shown by the asterisk) is removed from the scan recorded with excitation, it is clear that the subtracted emission (shown by the hash symbol) produced with excitation is identical to that produced with excitation. The vertical line indicates the position of the gas phase transition. The panel on the right-hand side shows a comparison of the emission decay curves recorded with excitation into the five spin-orbit levels of the state. All the decay curves are identical and long-lived, extending up to .

Image of FIG. 5.
FIG. 5.

Shown on the left is the decay profile of the emission feature recorded at using TCSPC following pulsed laser excitation at . The parameters extracted in the triple exponential fit are listed in the plot. The decay curve shown on the right was recorded for the emission and produced with the same excitation. The presence of a risetime on this decay is clearly evident in the triple exponential fit conducted. Also shown in this panel is the decay of the emission but produced with direct, blue site excitation at .

Image of FIG. 6.
FIG. 6.

laser excitation spectra recorded at , in the vicinity of the gas phase transition monitoring the red site and blue site emission features at 590 and , respectively. The sample was deposited at and annealed to .

Image of FIG. 7.
FIG. 7.

Laser excitation spectra recorded for at , with Rhodamine 590 and Rhodamine 610 monitoring emission at 590 and , respectively. The dashed vertical lines indicate the gas phase positions of the individual transitions (Ref. 3). Particularly noteworthy is the overlap of the excitation and emission scans recorded for the level at which provides an estimate of the zero phonon line for this transition. Also evident is a small red-shift of the entire excitation and emission bands from the gas phase positions.

Image of FIG. 8.
FIG. 8.

Shown on the left is the decay profile of the emission feature recorded at using TCSPC following pulsed laser excitation at , corresponding to excitation. The parameters extracted in the triple exponential fit are listed in the plot. The decay curve shown on the right was recorded for the emission and produced with the same excitation. The triple exponential fit conducted is also shown. Also shown on the right (with the dashed line) is the decay of the emission but produced with direct blue site excitation at .

Image of FIG. 9.
FIG. 9.

Laser excitation spectra recorded in at , with Rhodamine 590 and Rhodamine 610 monitoring emission at . The dashed vertical lines indicate the gas phase positions of the individual transitions (Ref. 3) shifted by . The broad spectral shapes of the excitation and emission bands contrast with the narrow structured bands recorded with Rh590. The presence of the latter bands is interpreted as the first indication of the existence of red site occupancy of Mn atoms in Xe matrices. However, the emission of this site was not detected in the present study.

Image of FIG. 10.
FIG. 10.

Shown on the left is the decay profile of the emission feature recorded at using TCSPC following pulsed laser excitation at . The parameters extracted in the triple exponential fit are listed in the plot. The decay curves shown on the right were recorded for the emission at the specified temperatures.

Image of FIG. 11.
FIG. 11.

A comparison of the red site excitation and emission spectra recorded in Ar, Kr and Xe matrices. The correspondence of the ZPLs in the system is evident as is the small Stokes shift in . The red site emission was not detected in the system. The excitation spectra shown were recorded with both Rhodamine 590 and 610.

Image of FIG. 12.
FIG. 12.

A comparison of the blue site excitation and emission spectra recorded in Ar, Kr and Xe matrices. All the excitation spectra were recorded with Rhodamine 610.

Tables

Generic image for table
Table I.

Details of the resolved excitation features recorded monitoring the red site emission bands in the red spectral region for the , and matrix systems. Spectral positions of the observed excitation features and the gas phase energies for the individual transitions are indicated in nanometer (nm) and wave number units for the individual spin-orbit levels. indicates the splitting between successive spin-orbit levels in the gas phase3 (GP) and is the splitting recorded for the three RG matrix systems. The shifts of the observed matrix bands are presented in wave number units.

Generic image for table
Table II.

Photophysical characteristics and excited state assignments of the red site emission features produced with direct excitation of the transitions of matrix-isolated atomic manganese in solid Ar and Kr. indicates the emission band center in nm and wavenumber units. The matrix shift from the gas phase (Ref. 3) transition at is indicated in wavenumber units by . The emission in Xe is presented with the blue site data of Ar and Kr in Table III. The dominant decay components are shown in bold font.

Generic image for table
Table III.

Photophysical characteristics of the blue site luminescence in Ar, Kr and Xe matrices. The excitation and emission maxima are quoted in wavelength (nm) and wavenumber units. The Stokes shifts measured in the three matrices are listed as in wavenumber units. All the emission bands listed are assigned to the state. The dominant decay components are shown in bold font.

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/content/aip/journal/jcp/123/4/10.1063/1.1961531
2005-08-02
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Luminescence spectroscopy of matrix-isolated atomic manganese: Excitation of the “forbidden” aDJ6↔aS6 transitions
http://aip.metastore.ingenta.com/content/aip/journal/jcp/123/4/10.1063/1.1961531
10.1063/1.1961531
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