Zero-field splitting spectroscopy

Notice that if the molecule has axial symmetry, Dxx = Dyy so that E=0. If the molecule has octahedral symmetry, Dxx = Dyy = Dzz so that D = E=0. Thus the appearance of a zero-field splitting into two or three levels tells the spectroscopist something about the symmetry of the molecule. It is possible, of course, to do spectroscopy on these energy levels at zero magnetic field. Our concern here is the effect of zero-field splitting on the ESR spectrum where a magnetic field is applied. 

EPR Spectroscopy. The structure of triplet carbenes is unequivocally characterized by EPR zero-field splitting (ZFS) parameters, which are analyzed by D and E values. In a simple model, the ZFS parameters D and E for a triplet depend on the distance between electrons with parallel spins as given by... 

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It is important to realize that no one method of spectroscopy is clairvoyant. Electron paramagnetic resonance spectroscopy cannot sense low-spin Fe(II) as this state is diamagnetic, nor reliably the high-spin Fe(II) state because of rapid spin-lattice relaxation, large zero-field splittings or both Mossbauer spectroscopy cannot distinguish Fe(III) spin states... 

Keywords Emission quantum yields High-resolution spectroscopy Iridium complexes OLED emitters Organometallic compounds Phosphorescence Photophysics Platinum complexes Radiative rates Spin-orbit coupling Triplet emitters Zero-field splitting SOC ZFS SOC and geometry SOC paths... 

The Spin Hamiltonian Formalism Determination of Zero-Field Splitting D and Rhombicity E/D of Paramagnetic Iron Centers by Mossbauer Spectroscopy... 

Mossbauer spectroscopy can also be used to obtain information about fine structure parameters like zero-field splitting D and rhombicity parameter E D. The zero-field splitting is a second-order effect, which can be classically visualized as resulting from the circular currents generated in the atomic shell by the electron spin. In Section 3.10.5, we describe how D and E D can be calculated. 

The results discussed above have shown that time-resolved emission spectroscopy can provide detailed insight into vibronic deactivation paths of triplet substates, even when the zero-field splitting is one order of magnitude smaller than the obtainable spectral resolution (= 2 cm ). This is possible at low temperature (1.3 K), because the triplet sublevels emit independently. They are not in a thermal equilibrium due to the very small rates of spin-lattice relaxation between these substates. In the next section, we return to this interesting property by applying the complementary methods of ODMR and PMDR spectroscopy to the same set of triplet substates. 

The information obtained from the phosphorescence microwave double resonance (PMDR) spectroscopy nicely complements the results deduced from time-resolved emission spectroscopy. (See Sect. 3.1.4 and compare Ref. [58] to [61 ].) Both methods reveal a triplet substate selectivity with respect to the vibrational satellites observed in the emission spectrum. Interestingly, this property of an individual vibronic coupling behavior of the different triplet substates survives, even when the zero-field splitting increases due to a greater spin-orbit coupling by more than a factor of fifty, as found for Pt(2-thpy)2. 

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