Fourier transform microwave spectroscopy of LiCCH, NaCCH, and KCCH: Quadrupole hyperfine interactions in alkali monoacetylides

Sheridan, P. M.; Binns, M. K. L.; Sun, Ming; Min, Jie; Bucchino, Matthew P.; Halfen, D. T.; Ziurys, L. M.

doi:10.1016/j.jms.2011.07.008

Cited by 12 publications

(4 citation statements)

References 27 publications

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“…On the other hand, the Li and Na eQq values are well described by our calculations and they are similar to those found experimentally for analogous molecules, such as the lithium and sodium acetylides. 43 Thus, the eQq values for Li and Na in the LiCCH and NaCCH systems, 0.375 MHz and -7.264 MHz, respectively, 43 are very close to our values of 0.3603 and -7.0497 MHz, respectively. Thus, Li-C and Na-C bond character in the LiCCCN and NaCCCN molecules are almost the same than those for LiCCH and NaCCH, which present a high degree of ionic metal–ligand bonding character similar to the halides or hydroxides while the covalent character of the metal–ligand bond is minimal, as it has been shown by Sheridan et al 43…”

Section: Discussionsupporting

confidence: 84%

Alkaline and alkaline-earth cyanoacetylides: A combined theoretical and rotational spectroscopic investigation

Cabezas

Barrientos

Largo

et al. 2019

The Journal of Chemical Physics

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The metallic cyanoacetylides LiC3N, NaC3N, MgC3N and CaC3N have been investigated by combined spectroscopy measurements and theoretical calculations. The theoretical calculations predict for the four species that the linear isomer with formula MCCCN (M= Li, Na, Mg and Ca) is the most stable one. We used the laser ablation molecular beam Fourier transform microwave spectroscopy to synthesize these species by the reaction of metal vapors, produced by laser ablation, and the 3-bromo-2-propynenitrile (BrCCCN). The pure rotational spectra were observed by Fourier transform microwave spectroscopy in the 2–18 GHz frequency region only for LiCCCN and NaCCCN, while no spectral signatures for MgCCCN and CaCCCN could be detected. Finally, we have searched for LiCCCN and NaCCCN species towards the carbon-rich evolved star IRC + 10216 but only upper limits to their abundances have been obtained.

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Section: Discussionsupporting

confidence: 84%

Alkaline and alkaline-earth cyanoacetylides: A combined theoretical and rotational spectroscopic investigation

Cabezas

Barrientos

Largo

et al. 2019

The Journal of Chemical Physics

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“…26 The reaction mixture consisted of 0.25% H 2 S in Ar, introduced at a stagnation pressure of 34 psi. Alkali metal vapor was created in the gas flow by ablating pure potassium metal, pressed onto a machined aluminum rod, 27 with the 2nd harmonic (532 nm) of a Nd:YAG laser (200 mJ/pulse). A 500 V DC discharge was then applied to the reactants.…”

Section: Experimental Methodsmentioning

confidence: 99%

Trends in alkali metal hydrosulfides: A combined Fourier transform microwave/millimeter-wave spectroscopic study of KSH ($\tilde X^1 A^\prime $X̃1A′)

Bucchino¹,

Sheridan²,

Young³

et al. 2013

The Journal of Chemical Physics

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The pure rotational spectrum of KSH (X(1)A') has been measured using millimeter-wave direct absorption and Fourier transform microwave (FTMW) techniques. This work is the first gas-phase experimental study of this molecule and includes spectroscopy of KSD as well. In the millimeter-wave system, KSH was synthesized in a DC discharge from a mixture of potassium vapor, H2S, and argon; a discharge-assisted laser ablation source, coupled with a supersonic jet expansion, was used to create the species in the FTMW instrument. Five and three rotational transitions in the range 3-57 GHz were recorded with the FTMW experiment for KSH and KSD, respectively, in the K(a) = 0 component; in these data, potassium quadrupole hyperfine structure was observed. Five to six transitions with K(a) = 0-5 were measured in the mm-wave region (260-300 GHz) for the two species. The presence of multiple asymmetry components in the mm-wave spectra indicates that KSH has a bent geometry, in analogy to other alkali hydrosulfides. The data were analyzed with an S-reduced asymmetric top Hamiltonian, and rotational, centrifugal distortion, and potassium electric quadrupole coupling constants were determined for both isotopolgues. The r0 geometry for KSH was calculated to be r(S-H) = 1.357(1) Å, r(K-S) = 2.806(1) Å, and θ(M-S-H) (°) = 95.0 (1). FTMW measurements were also carried out on LiSH and NaSH; metal electric quadrupole coupling constants were determined for comparison with KSH. In addition, ab initio computations of the structures and vibrational frequencies at the CCSD(T)/6-311++G(3df,2pd) and CCSD(T)/aug-cc-pVTZ levels of theory were performed for LiSH, NaSH, and KSH. Overall, experimental and computational data suggest that the metal-ligand bonding in KSH is a combination of electrostatic and covalent forces.

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“…Similarly, the closed d-subshell molecule, ZnCCH, which is also similar to the alkaline earth acetylides, has been studied by microwave and millimeter wave spectroscopy . Fourier transform microwave studies of the alkali acetylides LiCCH, − NaCCH, ,,, and KCCH , have also been reported. Among the p-block metals, AlCCH has been studied through matrix isolation, optical and FT microwave spectroscopy, and computational work. − Among the d-block metal acetylides, a Fourier transform microwave study of AgCCH has been reported .…”

Section: Introductionmentioning

confidence: 99%

Electronic Spectroscopy and Electronic Structure of Copper Acetylide, CuCCH

Díaz-García

Morse

2013

J. Phys. Chem. A

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The optical spectrum of the linear CuCCH molecule has been investigated for the first time, using resonant two-photon ionization spectroscopy employing ArF (193 nm) or F2 (157 nm) excimer radiation for photoionization. Scans over the range 19 400-25 200 cm(-1) were conducted, leading to the observation of three electronic band systems. These are identified as the [20.2] ã1 ← X̃ (1)Σ(+), the [23.1] Ã (1)Σ(+) ← X̃ (1)Σ(+), and the [24.7] B̃ (1)Π ← X̃ (1)Σ(+) systems, although only the first two have been rotationally resolved. The ã1 state is tentatively assigned as having (3)Π1 symmetry, becoming optically accessible through spin-orbit interaction with the B̃ (1)Π state. Vibrational assignments have provided the frequency of the Cu-C stretching mode, ν3, in the ground and all three excited states, along with both bending modes, ν4 and ν5, in the Ã (1)Σ(+) and B̃ (1)Π states, and the Cu-C≡C bending mode, ν5, in the ground state. Comparisons are made to the known electronic states of CuF, CuCl, CuBr, and CuI, and it is argued that like these molecules, the CuCCH molecule is essentially ionic in both the ground and excited states, with the ground state correlating diabatically to Cu(+) (3d(10), (1)S) + CCH(-) (X̃ (1)Σ(+)) and the excited states correlating diabatically to Cu(+) (3d(9)4s(1), (1,3)D) + CCH(-) (X̃ (1)Σ(+)).

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Fourier transform microwave spectroscopy of LiCCH, NaCCH, and KCCH: Quadrupole hyperfine interactions in alkali monoacetylides

Cited by 12 publications

References 27 publications

Alkaline and alkaline-earth cyanoacetylides: A combined theoretical and rotational spectroscopic investigation

Alkaline and alkaline-earth cyanoacetylides: A combined theoretical and rotational spectroscopic investigation

Trends in alkali metal hydrosulfides: A combined Fourier transform microwave/millimeter-wave spectroscopic study of KSH ($\tilde X^1 A^\prime $X̃1A′)

Electronic Spectroscopy and Electronic Structure of Copper Acetylide, CuCCH

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