TY - JOUR
T1 - Completing the 3d metal fluoride series
T2 - The pure rotational spectrum of ZnF (X2∑+)
AU - Flory, M. A.
AU - McLamarrah, S. K.
AU - Ziurys, L. M.
N1 - Funding Information:
The authors would like to thank Professor J. M. Brown for use of his fitting code and M. A. Brewster for helpful discussions. This work was supported by NSF Grant No. CHE 04-11551.
PY - 2006
Y1 - 2006
N2 - The pure rotational spectrum of the ZnF radical has been recorded in the range of 176-527 GHz using millimeter/submillimeter direct absorption techniques. This study is the first gas-phase spectroscopic investigation of this species. Between 5 and 11 transitions were measured for each of five isotopologues of this radical (Zn64 F, Zn66 F, Zn67 F, Zn68 F, and Zn70 F) in the ground and several excited vibrational (v=1, 2, and 3) states. Each transition consists of spin-rotation doublets with a splitting of ∼150 MHz, indicating that the electronic ground state of ZnF is +2, as predicted by theory. Fluorine hyperfine splitting was observed in three isotopologues (Zn64 F, Zn66 F, and Zn67 F), and hyperfine structure from the zinc-67 nucleus (I=52) was additionally resolved in Zn67 F. Rotational, fine structure, and F19 and Zn67 hyperfine constants were determined for ZnF, as well as equilibrium parameters. The bond length of the main isotopologue Zn64 F was calculated to be re =1.7677 Å. Evaluation of the hyperfine constants indicates that the orbital containing the unpaired electron is ∼80% 4s (Zn) in character with ∼10% contributions from each of the 2p (F) and 4p (Zn) orbitals. These results imply that ZnF is somewhat less ionic than CaF, as suggested by theory.
AB - The pure rotational spectrum of the ZnF radical has been recorded in the range of 176-527 GHz using millimeter/submillimeter direct absorption techniques. This study is the first gas-phase spectroscopic investigation of this species. Between 5 and 11 transitions were measured for each of five isotopologues of this radical (Zn64 F, Zn66 F, Zn67 F, Zn68 F, and Zn70 F) in the ground and several excited vibrational (v=1, 2, and 3) states. Each transition consists of spin-rotation doublets with a splitting of ∼150 MHz, indicating that the electronic ground state of ZnF is +2, as predicted by theory. Fluorine hyperfine splitting was observed in three isotopologues (Zn64 F, Zn66 F, and Zn67 F), and hyperfine structure from the zinc-67 nucleus (I=52) was additionally resolved in Zn67 F. Rotational, fine structure, and F19 and Zn67 hyperfine constants were determined for ZnF, as well as equilibrium parameters. The bond length of the main isotopologue Zn64 F was calculated to be re =1.7677 Å. Evaluation of the hyperfine constants indicates that the orbital containing the unpaired electron is ∼80% 4s (Zn) in character with ∼10% contributions from each of the 2p (F) and 4p (Zn) orbitals. These results imply that ZnF is somewhat less ionic than CaF, as suggested by theory.
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U2 - 10.1063/1.2355495
DO - 10.1063/1.2355495
M3 - Article
AN - SCOPUS:33845324892
SN - 0021-9606
VL - 125
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 19
M1 - 194304
ER -