X-ray absorption spectroscopy studies of spin–orbit coupling in 5d transition metal oxides

In order to examine the effects of strong valence band spin–orbit coupling (SOC) in 5d transition metal oxides (TMOs), we have investigated the L2 and L3 edge white-line intensities of the x-ray absorption spectra of several 5d TMOs. The white-line intensities at both edges are found to decrease monotonously with increasing 5d electron occupancy, while their ratio showed anomalous behavior for late 5d TMOs (IrO2, PtO2, and Au2O3), deviating significantly from the theoretical value of 2 expected for the case of weak SOC. This observation serves as a clear experimental indication of strong SOC effects in 5d TMOs. We also discussed how the 5d TMOs can have charge transfer effects different from their counterpart 5d elemental metals by making comparative studies. Our works demonstrate the importance of j quantum states due to strong SOC in the 5d system.

[1]  T. Sakakibara,et al.  Time-reversal symmetry breaking and spontaneous Hall effect without magnetic dipole order , 2010, Nature.

[2]  Gang Cao,et al.  Temperature dependence of the electronic structure of the J eff =(1)/(2) Mott insulator Sr 2 IrO 4 studied by optical spectroscopy , 2009 .

[3]  S. Sakai,et al.  Phase-Sensitive Observation of a Spin-Orbital Mott State in Sr2IrO4 , 2009, Science.

[4]  Jan Kunes,et al.  Quantum spin Hall effect in a transition metal oxide Na2IrO3. , 2008, Physical review letters.

[5]  Jaejun Yu,et al.  Novel Jeff=1/2 Mott state induced by relativistic spin-orbit coupling in Sr2IrO4. , 2008, Physical review letters.

[6]  W. Pompe,et al.  Density functional theory study of platinum oxides: From infinite crystals to nanoscopic particles , 2007 .

[7]  G. Laan,et al.  Anisotropic branching ratio in X-ray absorption spectra , 1997 .

[8]  Chen,et al.  X-ray-absorption studies of the d-orbital occupancies of selected 4d/5d transition metals compounded with group-III/IV ligands. , 1994, Physical review. B, Condensed matter.

[9]  Lu,et al.  Transition-metal (Au, Pt, Ir, Re) bonding to Al,Si,Ge: X-ray-absorption studies. , 1989, Physical review. B, Condensed matter.

[10]  Thole,et al.  Linear relation between x-ray absorption branching ratio and valence-band spin-orbit expectation value. , 1988, Physical review. A, General physics.

[11]  Thole,et al.  Local probe for spin-orbit interaction. , 1988, Physical review letters.

[12]  Thole,et al.  Multiplet structure in the L2,3 x-ray-absorption spectra: A fingerprint for high- and low-spin Ni2+ compounds. , 1988, Physical review. B, Condensed matter.

[13]  Ansari,et al.  L2 and L3 measurements of transition-metal 5d orbital occupancy, spin-orbit effects, and chemical bonding. , 1987, Physical review. B, Condensed matter.

[14]  Sham L-edge x-ray-absorption systematics of the noble metals Rh, Pd, and Ag and the main-group metals In and Sn: A study of the unoccupied density of states in 4d elements. , 1985, Physical review. B, Condensed matter.

[15]  I. Lindau,et al.  Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103 , 1985 .

[16]  P. Eisenberger,et al.  Extended x-ray absorption fine structure—its strengths and limitations as a structural tool , 1981 .

[17]  Peter G. Jones,et al.  Gold(III) oxide , 1979 .

[18]  L. Mattheiss Electronic structure of RuO 2 , OsO 2 , and IrO 2 , 1976 .

[19]  J. Bearden,et al.  REEVALUATION OF X-RAY ATOMIC ENERGY LEVELS. , 1967 .