EXTREME COVALENCE IN THE TC-CL BOND FROM POLARIZED NEUTRON-DIFFRACTION

被引：10

作者：

FIGGIS, BN ^{[1
]}

REYNOLDS, PA ^{[1
]}

CABLE, JW ^{[1
]}

机构：

[1] OAK RIDGE NATL LAB,DIV SOLID STATE,OAK RIDGE,TN 37831

来源：

JOURNAL OF CHEMICAL PHYSICS | 1993年 / 98卷 / 10期

关键词：

D O I：

10.1063/1.464581

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A polarized neutron diffraction experiment on a salt containing the 4d1 TcNCl4- ion (S=1/2) yielded the flipping ratios of six reflections confined to the hk0 plane. Using nuclear structure factors, F(N), extrapolated from the 123 and 295 K x-ray structures, magnetic structure factors, F(M), were obtained from the flipping ratios. The values of F(M) were fitted to a model of spin populations in the Tc-4d and the Cl-3(sp) orbitals. It was found that 46(5)% of the spin density is located on the Cl atoms, corresponding to exceptionally high covalence in the Tc-Cl bonding. The amount is distinctly higher than found indirectly by ESR measurements, but is to some extent supported by a local density functional DV-Xalpha calculation. Because the data is limited to the one projection, it is not possible to separate the Tc and N spin density contributions.

引用

页码：7743 / 7745

页数：3

共 11 条

[1] STUDIES OF TECHNETIUM COMPLEXES .6. THE PREPARATION, CHARACTERIZATION, AND ELECTRON-SPIN RESONANCE-SPECTRA OF SALTS OF TETRACHLORO-NITRIDOTECHNETATE(VI) AND TETRABROMO-NITRIDOTECHNETATE(VI) - CRYSTAL-STRUCTURE OF TETRAPHENYLARSONIUM TETRACHLORONITRIDOTECHNETATE(VI) [J].