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>lsquo;lsquo;White linesrsquo;rsquo; in the chlorineKxhyphen;ray absorption spectra of osmium(IV), iridium(III), iridium(IV), and platinum(IV) hexachlorides
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lsquo;lsquo;White linesrsquo;rsquo; in the chlorineKxhyphen;ray absorption spectra of osmium(IV), iridium(III), iridium(IV), and platinum(IV) hexachlorides
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机译：lsquo;lsquo;White linesrsquo;rsquo; in the chlorineKxhyphen;ray absorption spectra of osmium(IV), iridium(III), iridium(IV), and platinum(IV) hexachlorides
The chlorineKabsorption spectra from K2OsCl6, K2IrCl6, K2PtCl6, (NH4)2OsCl6, (NH4)3IrCl6, (NH4)2IrCl6, and (NH4)2PtCl6have been measured and explained in terms of molecularhyphen;orbital (MO) theory. Two conspicuous lsquo;lsquo;white linesrsquo;rsquo; have been observed at the absorption threshold of the spectra of the iridium(IV) and osmium(IV) hexachlorides in contrast to one intense white line in the spectra of the platinum(IV) and iridium(III) hexachlorides. The latter white line is ascribed to the electronic transition from the Cl 1score level to the lowest unoccupied antibonding MOeg(sgr;ast;) for the octahedral complex ions lsqb;PtCl6rsqb;2minus;and lsqb;IrCl6rsqb;3minus;and the former white lines are attributed to the transitions to the unoccupied MOrsquo;seg(sgr;ast;) andt2g(pgr;ast;) for the octahedral complex ion lsqb;IrCl6rsqb;2minus;or lsqb;OsCl6rsqb;2minus;. The energy differences between theeg(sgr;ast;) andt2g(pgr;ast;) orbitals for the complex ions lsqb;OsCl6rsqb;2minus;and lsqb;IrCl6rsqb;2minus;are estimated to be 1.8 and 1.9 eV, respectively. These white lines show the chemical shifts toward higher energies in the order of the platinum(IV) iridium(IV) iridium(III) osmium(IV) hexachlorides. The other absorption structures are broad and are quite alike throughout seven hexachlorides. The chlorineKabsorption spectra of the hexachlorides are little influenced by the exchange of the counterions K+and NH4+.
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