TY - JOUR
T1 - The rotational spectrum of CuCCH (X̃ 1∑+)
T2 - A Fourier transform microwave discharge assisted laser ablation spectroscopy and millimeter/submillimeter study
AU - Sun, M.
AU - Halfen, D. T.
AU - Min, J.
AU - Harris, B.
AU - Clouthier, D. J.
AU - Ziurys, L. M.
N1 - Funding Information:
This research is supported by NSF Grant No. CHE 07-18699. D.J.C. also thanks the NSF for support and the Ziurys group for their hospitality during his sabbatical leave.
PY - 2010/11/7
Y1 - 2010/11/7
N2 - The pure rotational spectrum of CuCCH in its ground electronic state (X̃ 1∑+) has been measured in the frequency range of 7-305 GHz using Fourier transform microwave (FTMW) and direct absorption millimeter/submillimeter methods. This work is the first spectroscopic study of CuCCH, a model system for copper acetylides. The molecule was synthesized using a new technique, discharge assisted laser ablation spectroscopy (DALAS). Four to five rotational transitions were measured for this species in six isotopologues (63CuCCH, 65CuCCH, 63Cu 13CCH, 63Cu 13CH, 63Cu 13CCH, and 63CuCCD); hyperfine interactions arising from the copper nucleus were resolved, as well as smaller splittings in CuCCD due to deuterium quadrupole coupling. Five rotational transitions were also recorded in the millimeter region for 63CuCCH and 65CuCCH, using a Broida oven source. The combined FTMW and millimeter spectra were analyzed with an effective Hamiltonian, and rotational, electric quadrupole (Cu and D) and copper nuclear spin-rotation constants were determined. From the rotational constants, an rm2 structure for CuCCH was established, with r Cu-C =1.8177 (6) Å, rC-C =1.2174 (6) Å, and rC-H =1.046 (2) Å. The geometry suggests that CuCCH is primarily a covalent species with the copper atom singly bonded to the CCH moiety. The copper quadrupole constant indicates that the bonding orbital of this atom may be sp hybridized. The DALAS technique promises to be fruitful in the study of other small, metal-containing molecules of chemical interest.
AB - The pure rotational spectrum of CuCCH in its ground electronic state (X̃ 1∑+) has been measured in the frequency range of 7-305 GHz using Fourier transform microwave (FTMW) and direct absorption millimeter/submillimeter methods. This work is the first spectroscopic study of CuCCH, a model system for copper acetylides. The molecule was synthesized using a new technique, discharge assisted laser ablation spectroscopy (DALAS). Four to five rotational transitions were measured for this species in six isotopologues (63CuCCH, 65CuCCH, 63Cu 13CCH, 63Cu 13CH, 63Cu 13CCH, and 63CuCCD); hyperfine interactions arising from the copper nucleus were resolved, as well as smaller splittings in CuCCD due to deuterium quadrupole coupling. Five rotational transitions were also recorded in the millimeter region for 63CuCCH and 65CuCCH, using a Broida oven source. The combined FTMW and millimeter spectra were analyzed with an effective Hamiltonian, and rotational, electric quadrupole (Cu and D) and copper nuclear spin-rotation constants were determined. From the rotational constants, an rm2 structure for CuCCH was established, with r Cu-C =1.8177 (6) Å, rC-C =1.2174 (6) Å, and rC-H =1.046 (2) Å. The geometry suggests that CuCCH is primarily a covalent species with the copper atom singly bonded to the CCH moiety. The copper quadrupole constant indicates that the bonding orbital of this atom may be sp hybridized. The DALAS technique promises to be fruitful in the study of other small, metal-containing molecules of chemical interest.
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U2 - 10.1063/1.3493690
DO - 10.1063/1.3493690
M3 - Article
C2 - 21054026
AN - SCOPUS:78650637545
SN - 0021-9606
VL - 133
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 17
M1 - 174301
ER -