Spectra and Structures for Group 4 Di- and Tetrahydroxides
J. Phys. Chem. A, Vol. 109, No. 47, 2005 10701
cm-1).34 On the other hand, the ionic Zr(OH)4 molecule is even
more ionic than Hf(OH)4, consistent with the slightly lower
ionization energy of Zr compared to Hf.30 Finally, Zr(OH)4 and
Hf(OH)4 are computed to be very stable tetrahedral molecules.
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Conclusions
Hafnium and zirconium atoms react with H2O2 and with H2
+ O2 mixtures in solid argon to form the M(OH)2 and M(OH)4
molecules, which are identified from matrix infrared spectra
with the assistance of isotopic substitution. Electronic structure
calculations at the MP2 level predict almost linear and tetra-
hedral molecules, respectively, and frequencies for mixed
isotopic molecules of lower symmetry that are in excellent
agreement with observed values, which confirms the identifica-
tion of these hafnium and zirconium dihydroxide and tetrahy-
droxide molecules. In particular, the observation of resolved
O-D stretching modes for the four isotopic molecules M(OH)3-
(OD), M(OH)2(OD)2, M(OH)(OD)3, and M(OD)4 for Hf and
Zr conclusively identifies these tetrahydroxide molecules. Our
observations show that these structures are tetrahedral or nearly
tetrahedral. Titanium reacts to give the same products, but Ti-
(OH)4 has the S4 structure with bent Ti-O-H bonds, and Ti-
(OH)2 appears to be nearly linear. This work reports definitive
evidence for Group 4 dihydroxides and tetrahydroxides, which
are the first examples of metal tetrahydroxide molecules.
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Acknowledgment. We gratefully acknowledge financial
support from NSF Grant CHE03-53487, helpful e-mail cor-
respondence with L. Khriachtchev, S. Pehkonen, P. Pyykko,
and M. Zhou, and Figure 7 kindly provided by M. Zhou.
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