Abstract
Polarized S K- and L-edge, Mo L3- and L2-edge x-ray absorption near-edge structure (XANES) of natural molybdenite (2H-MoS2) have been measured with synchrotron radiation. These results are qualitatively interpreted using the energy band model of molybdenite and provide important information on the unoccupied states of molybdenite. The valence band (VB) maximum of molybdenite is characterized by fully occupied Mo 4dz 2, and the conduction band (CB) minimum of molybdenite is characterized by unoccupied Mo 4d states. The unoccupied Mo 4d band is split into two sub-bands, designated as t −2g /t +2g and e −g /e +g sets. Although the relative energy of these two sets are difficult to be evaluated, probably the former has the lower energy than the latter, both two sets have the combination wave functions of the other unoccupied Mo 4d components, rather than the simple 4dx 2 — y2 and 4dxy states. The unoccupied Mo 4d sub-bands contain significant DOS of both S 3 p- and 3 s-like states, indicating strong hybridization with S 3s and 3 p states. In the lower energy sub-band, the DOS of the S pz- and px,y-like states are very similar. However, in the higher energy sub-band, the DOS of the S 3 px,y-like state is lower than that of the S 3pz state. Polarized S K-edge XANES also reveal the features of antibonding S pz- and px,y-like states in molybdenite. The feature assigned to the S 3 pz-like states is stronger and sharper, and shifts to lower energy by about 2 eV relative to that for the S 3 px,y-like states.
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Abbati I, Braicovich L, Carbone C, Nogami J, Lindau I, Del Pennino U (1986) Synchrotron radiation study of the photoionization cross sections for the whole valence band of 2H-MoS2. J Electron Spectrosc Relat Phenom 40:353–362
Ballhausen CJ (1962) Introduction to ligand Field Theory. McGraw-Hill, New York
Bancroft GM (1992) New developments in far UV, soft x-ray research at the Canadian synchrotron radiation facility. Can Chem News 44:15–22
Bullett DW (1978) Electronic band structure and bonding in transition metal layered dichalcogenides by atomic orbital method. J Phys C Solid-State Phys 11:4501–4514
Calais JL (1977) Band structure of transition metal compounds. Adv Phys 26:847–885
Coehoorn R, Haas C, Dijkstra J, Flipse CJF, de Groot RA, Wold A (1987) Electronic structure of MoSe2, MoS2, and WSe2. I. Band structure calculations and photoelectron spectroscopy. Phys Rev B 35:6195–6202
Haycock DE, Urch DS, Wiech G (1979) Electronic structure of molybdenum disulfide. J Chem Soc Faraday Trans II 75:1692–1702
Heald SM, Stern EA (1977) Anisotropic x-ray absorption in layered compounds. Phys Rev B16:5549–5559
Kasowski RV (1973) Band structure of MoS2 and NbS2. Phys Rev Lett 30:1175–1178
Kasrai M, Fleet ME, Sham TK, Bancroft GM, Tan KH, Brown JR (1988) A XANES study of the S L-edge in sulfide minerals: application to interatomic distance determination. Solid-State Commun 68:507–511
Mamy R, Boufelja A, Carricaburu B (1987) Angle resolved photoemission and electronic band structure of MoS2. Phys Status Solidi B141:467–473
Mattheiss LF (1973) Band structures of transition-metal-dichalcogenide layer compounds. Phys Rev B8:3719–3740
McGovern IT, Williams RH, Parke AW (1979) The electronic structure of MoS2 and α-MoTe2 by photoelectron spectroscopy using line and synchrotron sources. J Phys C Solid-State Phys 12:2689–2704
McGovern IT, Childs KD, Clearfield HM, Williams RH (1981) Atomic effects in the photoemission cross sections of the valence states of MoS2. J Phys C Solid-State Phys 14:L243-L246
McMenamin JC, Spicer WE (1977) Photoemission studies of layered transition-metal dichalcogenides: MoS2. Phys Rev B16:5474–5487
Müller W, Wiech G, Šimůnek A (1983) Angle-dependent x-ray emission bands of sulfur in SnS2 and MoS2. Phys Lett 98A: 66–68
Ohno Y (1987) Primary-energy dependence of the momentum transfer in reflection inner-shell-electron energy-loss spectra of layered transition-metal dichalcogenides. Phys Rev B 36:7500–7509
Ohno Y, Hirama K, Nakai S, Sugiura C, Okada S (1983a) X-ray absorption spectroscopy of layer transition-metal disulfides. Phys Rev B27:3811–3820
Ohno Y, Hirama K, Nakai S, Sugiura C, Okada S (1983b) X-ray absorption spectroscopy of layered 4d transition-metal dichalcogenides. J Phys C Solid-State Phys 16:6695–6701
Rosenberg RA, Love PJ, Rehn V (1986) Polarization-dependent C (K) near-edge x-ray-absorption fine structure of graphite. Phys Rev 33:4034–4037
Sancrotti M, Braicovich L, Chemelli C, Trezzi G (1988) The empty electron-states in MoS2: An inverse photoemission spectroscopy investigation. Solid State Commun 66:593–596
Šimůnek A, Wiech G (1984) Angle-dependent x-ray sulfur K-emission bands and electronic structure of SnS2 and MoS2. Phys Rev B 30:923–930
Sonntag B, Brown FC (1974) Soft x-ray response of transition-metal layer compounds. Phys Rev B10:2300–2306
Sugiura C, Suzuki I, Kashiwakura J, Gohshi Y (1976) Sulfur 128–01 x-ray emission bands and valence-band structures of transition metal disulfides. J Phys Soc Jap 40:1720–1724
Wertheim GK, DiSalvo FJ, Buchanan DNE (1973) Valence bands of layer structure transition metal chalcogenides. Solid-State Commun 13:1225–1228
Wilson JA, Yoffe AD (1969) The transition metal dichalcogenides: Discussion and interpretation of the observed optical, electrical and structural properties. Adv Phys 18:193–335
Wood K, Pendry JB (1973) Layer method for band structure of layer compounds. Phys Rev Lett 31:1400–1403
Yang BX, Middleton FH, Olsson BG, Bancroft GM, Chen JM, Sham TK, Tan KH, Wallace DJ (1992) The design and performance of a soft x-ray double crystal monochromator beamline at Aladdin. Nucl Inst Method Phys Res A316:422–436
Yarmoshenko YuM, Cherkashenko VM, Kurmaev EZ (1983) The anisotropy of x-ray emission spectra for 2H-MoS2 single crystals. J Electron Spectrosc Relat Phenom 32:103–112
Yu XR, Liu F, Wang ZY, Chen Y (1990) Auger parameters for sulfur-containing compounds using a mixed aluminum-silver excitation source. J Electron Spectrosc Relat Phenom 50:159–166
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Li, D., Bancroft, G.M., Kasrai, M. et al. Polarized X-ray absorption spectra and electronic structure of molybdenite (2H-MoS2). Phys Chem Minerals 22, 123–128 (1995). https://doi.org/10.1007/BF00202472
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DOI: https://doi.org/10.1007/BF00202472