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Femtosecond electronic relaxation of excited metalloporphyrins in the gas phase
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10.1063/1.2176612
/content/aip/journal/jcp/124/11/10.1063/1.2176612
http://aip.metastore.ingenta.com/content/aip/journal/jcp/124/11/10.1063/1.2176612

Figures

Image of FIG. 1.
FIG. 1.

(a) Formula of metal-5,10,15,20-tetraphenylporphine , . (b) Formula of metal-2,3,7,8,12,13,17,18-octaethylporphine , .

Image of FIG. 2.
FIG. 2.

Electron kinetic energy release (KER) spectrum of ZnTPP obtained under pump/probe conditions. (a) Integration over all delay times. This photoelectron spectrum can be analyzed as an overlap of two broadbands (dotted lines). (b) Integration over short delay times between zero and . The relative intensity of the two broadbands (dotted line) varies with the pump and probe delays. (c) Integration over long delays between 2800 and .

Image of FIG. 3.
FIG. 3.

Time evolution of the electron KER spectrum of ZnTPP obtained under pump/probe conditions . (a) At , the decay of the photoelectron signal can be fitted by forward convolution with a laser pulse to a rise superimposed on an instant growth. Both contributions have equal weights in the fit (see text). (b) At the decay of the photoelectron signal can be fitted by forward convolution with a laser pulse to a biexponential function with a constant and a longer decay and weightings of 0.95% and 5%.

Image of FIG. 4.
FIG. 4.

(a) Time evolution of while scanning the pump/probe delay . The signal can be fitted by forward convolution with a laser pulse to a biexponential function with time constants of 65 and and weightings of 75% and 25%, respectively. (b) Time evolution of while scanning the pump/probe delay . The signal can be fitted by forward convolution with a laser pulse to a biexponential function with time constants of 100 and and weightings of 80% and 20%, respectively.

Image of FIG. 5.
FIG. 5.

Time evolution of and and . In the figure MP stands for RuOEP. (a) Time-of-flight mass spectrum of RuOEP following photoionization, integrated over all pump and probe delays. Ion signals as a function of the time delay between the pump and the probe . (b) recorded at the mass of parent molecules [RuOEP CO], (c) the observation is set at the RuOEP mass, and (d) . The experimental points are fitted by the solid line following a three level model described in the text. The contributions of each component are represented by dashed curves. The dotted curve indicates the cross correlation of the pump and probe pulses.

Image of FIG. 6.
FIG. 6.

Comparison of the electron kinetic release spectra of CuTPP (solid line) and ZnTPP (dashed line) obtained under different pump/probe conditions . (a) Taken at pump/probe delays close to zero, the spectra are very similar in extension and shape, bimodal. The dashed curves represent the extension of the electron spectrum of towards the zero of energy, as deduced from the instant contribution in the decay profiles. (b) At long pump/probe delays the spectrum of CuTPP is concentrated around , while in the case of ZnTPP, the spectrum is broad with a sharp cutoff at .

Image of FIG. 7.
FIG. 7.

Schematic representation of the relaxation pathway of ZnTPP excited in the state.

Image of FIG. 8.
FIG. 8.

Energy levels of separated TPP and Ni metal orbitals in the ligand field approximation (from Fig. 2 of Ref. 38). This scheme describes the mechanism of the relaxation pathway of the excited state. (1) Excitation. (2) Ultrafast charge transfer from the porphyrin ring to the orbital of the metal, likely via a conical intersection. This decay is followed at longer times by (3), a back transfer from the metal to the empty porphyrin orbital .

Tables

Generic image for table
Table I.

Decay lifetimes of the excited state of different metalloporphyrins: -TPP or -OEP.

Generic image for table
Table II.

Decay lifetimes and relative amplitudes of [RuOEP CO] excited at and its fragments, , as obtained from Eq. (1).

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/content/aip/journal/jcp/124/11/10.1063/1.2176612
2006-03-16
2014-04-25
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Femtosecond electronic relaxation of excited metalloporphyrins in the gas phase
http://aip.metastore.ingenta.com/content/aip/journal/jcp/124/11/10.1063/1.2176612
10.1063/1.2176612
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