Atomic and molecular spin-orbit coupling constants for 3d transition metal ions

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)5MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

“…† We have neglected the triplet excited states as the spin-orbit coupling parameter for chromium(0) is small and direct population of triplet excited states is consequently unlikely under the conditions used in our experiments. 15,32 These data indicate that the anti-isomer is only marginally more stable (7 kJ mol −1 ) than the syn-isomer in the ground state and that the two isomers are separated by a thermal barrier of approximately 60 kJ mol −1 . Variable temperature 1 H NMR studies estimated this barrier as 57 kJ mol −1 in dichloromethane solution (see ESI for details †).…”

“…14 This, in turn, was reported to yield a triplet metallaketene species which relaxes to the singlet surface by coordination of a molecule of solvent. Given the small spin-orbit coupling of chromium 15 and the proposal that the triplet metallaketene reacts with the singlet solvent molecule, 16 it is important to present additional experimental results to provide a fuller understanding of the photophysical and photochemical processes underpinning this important reaction.…”

Low-temperature magnetic ordering and structural distortions in vanadium sesquioxideV2O3

“…Such a magnetic anisotropy is, at first glance, not expected for a light element like Vanadium. However, for similar compounds like Vanadium spinels, values of spinorbit coupling in the range of 13-20 meV have been reported [34][35][36][37] , which makes a DFT calculation including relativistic effects (spin-orbit coupling) and noncollinear magnetism worth trying. To this end, the implementation thereof 38 in Quantum ESPRESSO has been used with a fully relativistic pseudopotential (V.rel-pbe-spnl-rrkjus psl.1.0.0.UPF from the PSLibrary of http://www.quantum-espresso.org) and the rotationally invariant GGA+U formulation of Liechtenstein et al 39 .…”

Excited state potential energy surfaces and their interactions in FeIVO active sites

“…The in-state SOC between the spatially two-fold degenerate components of the LF 5 E state (depicted in Figure 5B) is effectively controlled by the z-component of the SOC operator λ S z L z (where λ is a many-electron state-specific SOC constant) by acting on wavefunctions $|M_{\mathrm{L}}^{\text{eff}}=\pm 1,M_S=0,\pm 1,\pm 2\rangle$, where the effective magnetic quantum number $M_{\mathrm{L}}^{\text{eff}}$ reflects the one-electron configuration subspace $d_{\text{xz}}^0{d}_{\text{yz}}^1,d_{\text{xz}}^1{d}_{\text{yz}}^0$ of the LF 5 E . This SOC produces five two-fold degenerate sublevels of the LF 5 E state with an energy separation between the lower-energy LCP and higher-energy RCP state of 2λ = 2(ζ 3d /4) = 260 cm −1 (ζ 3d is the one-electron SOC constant for Fe IV : 520 cm −1 ) 38 , as shown in Figure 5C. The relation λ = ζ/4 for this case is given by equation 3: $$\langle M_{\mathrm{L}}^{\text{eff}}=+1,M_{\mathrm{S}}=2\left|\mathrm{normal\lambda }{L}_{\mathrm{z}}{S}_{\mathrm{z}}\right|M_{\mathrm{L}}^{\text{eff}}=+1,M_{\mathrm{S}}=2\rangle =\langle \frac{1}{\sqrt{2}}false(d_{\text{yz}}+{id}_{\text{xz}}false)\mathrm{normal\alpha }\left|{\mathrm{\zeta }}_{3\mathrm{normald}}{l}_{\mathrm{z}}{s}_{\mathrm{z}}\right|\frac{1}{\sqrt{2}}\left(d_{\text{yz}}-i{d}_{\text{xz}}\right)\mathrm{normal\alpha }\rangle$$…”