Spectral excitation spectrum

Fig. 9. Calculated relative energies (in kK) of the most important MO s (a) and spectral excitation energies derived from the electronic absorption spectrum (b) of ClFe(Et2

Figure 4.37a represents the time-resolved luminescence spectrum of a hydrozincite under 266 nm laser excitation. A relatively broad band is detected at 430 nm, which is responsible for the well-known blue hydrozindte luminescence. Its spectral position and decay time of approximately 700 ns are typical for Eu luminescence. However, the excitation spectrum of this band consists of one narrow band at 240 nm (Fig. 4.37b), which does not correspond to an Eu " excitation spectrum. Two bands usually characterize the latter with relatively small Stokes shifts of 30-50 nm caused by crystal field splitting of the 4/ 5d-levels. Moreover, the measured Eu concentrations in the hydrozincite samples under investigation are very low (less than 0.5 ppm) and they do not correlate with the intensity of the blue luminescence, i.e. the band at 430 nm. 

Under short-waved UV lamp excitation (254 nm) visually observed luminescence of calcite is violet-blue with very long phosphorescence time of several seconds. Under long-waved UV lamp excitation (365 nm) calcite exhibits visually the same violet-blue luminescence as under 254 nm excitation, but long phosphorescence is not detected. Under short laser excitations, such as 266 and 355 nm, at 300 K calcite demonstrates intensive UV-violet emission band peaking at 415 nm with half-width of 55 nm (Fig. 5.76a). Excitation spectrum of this band is composed of short waved tail in the spectral range less... 

Excitation of the Eu3+ or Tb3+ ions has traditionally been indirect, by broad-band UV excitation of a conjugated organic ligand which is followed by intramolecular energy transfer to the lanthanide ion / system, followed in turn by /- / emission.614 However, more recently, following the advent of tunable dye lasers, direct excitation of an excited / level is in many cases preferable. By scanning this frequency, an excitation spectrum can be obtained whose energy values are independent of the resolution of a monochromator and not subject to spectral interferences. 

In contrast to the preceding set-up, spectrofluorimeters record an entire fluorescence spectrum. Each of the two motorised monochromators can scan a spectral band. It is possible to record the emission spectrum while maintaining a constant excitation wavelength or to record the excitation spectrum while maintaining a constant emission wavelength. Spectra often show small differences when they are obtained using different instruments. 

We demonstrate the Mil method, which couples the sensitivity of multiphoton excitation on the spectral phase of the laser pulses to probe microscopic chemical environment-induced changes in the multiphoton excitation spectrum of sensitive reporter molecules. We carry out the optimization of the required phase functions in solution and provide theoretical simulations. We show experimental images whereby pH-selective two-photon microscopy is achieved and demonstrate how selective excitation can be used to enhance contrast and, consequently, to achieve functional imaging, using fluorescent probes sensitive to changes in their local environment. 

Figure 13-5. Mass-selected R2PI and population labeling spectra of guanine, 7MG and 9MG in the near UV region (310-280 nm). See text for details. Corresponding assignments are given in the insert. Tautomers indicated in gray are not observed in these experiments. Part of the fluorescence excitation spectrum is also shown in the spectral region where quenching occurs...

Excitation spectrum Plot of the spectral radiant exitance or of the spectral photon exitance against the frequency (or wavenumber, or wavelength) of excitation. When corrected for wavelength dependent variations in the excitation radiant power this is called a corrected excitation spectrum. 

Fig. 23. Time-resolved excitation spectra of Pt(2-thpy)2 in an n-octane matrix at T=1.3 K. (a) Time-resolved detection of the emission with no delay time and with an integration time (time window) of At = 2 ps. (b) Time-resolved detection of the emission with a delay time of t = 10 ps and a time window of At = 250 ps. The emission is detected at 16,444 cm" widi a spectral bandwidth of = 3 cm This allows us to monitor the vibrational satellites at origin I -713 cm" (A 16,443 cm" ) and at origin II - 718 cm" (A 16,445 cm" ) simultaneously. The spectra are normalized with respect to the intensity of origin II. The spectra are only reproduced up to = 720 cm from the electronic origins, but the same intensity ratio for the vibrational satellites of 2.2 0.2 (see text) is found for the whole range of our measurements up to = 1500 cm. (Compare also the time-integrated excitation spectrum shown in Fig. 15 and Ref [60])...

Fig. 28. Excitation spectra of Pt(2-thpy)2 dissolved in n-octane (a) at zero magnetic field and T = 4.2 K and (b) for different magnetic fields at T = 1.5 K. Concentration = 10 mol/1. For detection, the energy of 16,444 cm with a band width of = 5 cm was used, in order to monitor simultaneously the 713 cm and 718 cm vibrational satellites that correspond to the emissions of the triplet substates I and II, respectively. Under magnetic fields (b), the detection energy is red-shifted according to the size of the field-induced red shift of these satellites. The total excitation spectrum is composed of different spectra. The spectral resolution of the equipment is = 5 cm and = 160 cm for energies below and above the vertical line near 22,300 cm respectively. Note, the halfwidth given in (b) refers to the fwhm of a Lorentzian line shape function which was fit to the red flank of the corresponding peak. (Compare also to the Refs. [74] and [95])...

An increase in excitation of the fluorophore depends on the spectral overlap between the SPR and the excitation spectrum of the molecule and on the enhancement of the local field which, as can be seen below, depends on the position of the fluorophore and its distance from the metal surface. The distribution of the local (enhanced) fields for a nanoprism and nanorod are illustrated in Figure 11.11 [S]. The largest field intensities occur at the tips of the nanoprism and at the ends of the nanorods. The field intensities are calculated to be approximately 4000 times the applied field. These field enhancements are much larger than can be obtained with spheres. Even larger field oihancements can be obtained at the interface of nanoparticles in very close proximity to one another, as shown in Figure 11.12 [5]. 

The fluorescence polarization excitation spectrum has been measured for thymine in aqueous solution. " The depolarization at the red edge is attributed to the hidden n, ir transition. Ionization of the lowest excited singlet and triplet states have been determined by the effect of pH on the absorption, fluorescence, and phosphorescence spectra of purines and pyrimidines. " Spectral, polarization, and quantum yield studies of cytidylyl-(3, 5 )-adenosine have also been published. Intermediates in the room-temperature flash photolysis of adenine and some of its derivatives have been identified hydrated electron, radical cations and anions, and neutral radicals resulting from their reactions have been assigned. Photoionization occurs via the triplet state. FMN encapsulated in surfactant-entrapped water pools interacts with polar head groups, entrapped water molecules, and outer apolar solvent. ... 

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