Born-Oppenheimer breakdown effects and hyperfine structure in the rotational spectra of SbF and SbCl

Cooke, Stephen A.; Gerry, Michael C. L.

doi:10.1016/j.jms.2005.08.003

Cited by 18 publications

(9 citation statements)

References 51 publications

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“…Thus, only the MOs of SbCl n (n = 1–5) and SbCl n − ( n = 1–6) are shown in Figure 2. The optimized bond lengths of the 3 ∑ − state of SbF and SbCl obtained using CCSD(T)/AVQZ are in excellent agreement with the experimental values 26 . In addition, the bond length of the 3 ∑ − state of SbCl optimized using CCSD(T)/AVQZ is almost the same as that obtained using the multireference configuration interaction with Davidson correction (MRCI+Q)/aug‐cc‐pwCVQZ‐DK (Sb) + aug‐cc‐pVQZ‐DK (Cl) 27…”

Section: Resultssupporting

confidence: 72%

“…The harmonic vibrational frequencies of SbX (X = F and Cl) calculated using CCSD(T)/AVTZ are slightly underestimated compared with the experimental values (Table 2). 26 This underestimation may be attributed to the size of the triple‐ζ basis sets. We used AVQZ basis sets to examine the basis set effect on the vibrational frequencies in the CCSD(T) calculations.…”

Section: Resultsmentioning

confidence: 99%

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Theoretical study on molecular properties of SbX_n (X = F and Cl, n = 1–5) and SbX_n⁻ (X = F and Cl, n = 1–6) including spin–orbit coupling

Lee

Kim

2022

Bulletin Korean Chem Soc

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High-level ab initio and density functional theory (DFT) calculations were performed to calculate the molecular properties of SbX n (X = F and Cl, n = 1-5) and SbX n À (X = F and Cl, n = 1-6), such as molecular structure, vibrational frequency, electron affinity (EA), and bond dissociation energy (BDE). The spin-orbit (SO) effect on the molecular properties was investigated using the SODFT method. The bond lengths optimized by the coupled-cluster singles and doubles with perturbative triples method are in good agreement with the experimental values. The calculated vibrational frequencies agreed reasonably well with the available experimental values except for those of SbX 4 À (X = F and Cl) because the polar solvent affected the experimental results. SbX 3 and SbX 4 À (X = F and Cl), whose Sb oxidation states are +3, exhibit substantial EAs and BDEs, respectively. The SO effect on SbX À and SbX 2 À (X = F and Cl) was considerable.

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Section: Resultssupporting

confidence: 72%

Section: Resultsmentioning

confidence: 99%

Theoretical study on molecular properties of SbX_n (X = F and Cl, n = 1–5) and SbX_n⁻ (X = F and Cl, n = 1–6) including spin–orbit coupling

Lee

Kim

2022

Bulletin Korean Chem Soc

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“…However, since the ∆ 01 coefficients are usually comparable in magnitude for the two atoms [17], the value of ∆ N 01 can be assumed equal to that of ∆ H 01 . A more realistic assumption is ∆ N 01 = ∆ H 01 ± 1, as proposed by Cooke and Gerry [18]. In such a case the results are: has been taken into account too.…”

Section: Resultsmentioning

confidence: 99%

“…In this case, where the equilibrium distance has been derived only for two isotopologues, we approximate Eq. (18) to the following pair of equations:…”

Section: Resultsmentioning

confidence: 99%

Fine and hyperfine structure of the transition of ND in vibrational excited states

Dore

Bizzocchi²,

Esposti

et al. 2011

Molecular Physics

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The deuterated radical ND was produced in a DC discharge cell cooled at liquid nitrogen temperature. The discharge proved to be vibrationally hot, therefore the transient species could be detected in its vibrational excited states up to v = 6. By scanning in the 431-531 GHz frequency region, several fine-structure components of the N = 1 ← 0 transition in vibrational excited states were observed, each of them showing a complex hyperfine structure. A global analysis, including the measured frequencies and previous submillimeter-wave and infrared data, allowed an accurate determination of the equilibrium spectroscopic parameters of the ND radical including fine and hyperfine constants. A very precise determination of the equilibrium bond length re was obtained. This value is not consistent with the value reported in literature from NH data. This incongruity was discussed in terms of the breakdown of the Born-Oppenheimer approximation. In view of the recent detection of ND in a solar-mass protostar (A. Bacmann et al., Astron. Astrophys. 521, L42 (2010)), an extended spectroscopic characterization of this deuterated isotopologue of the NH species may prove useful, considering the large deuterium enhancement observed in molecular clouds.

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“…First application of this technique was done by the NIST group to study SiC 2 [46]. Since then many metal oxides and solid organic compounds have been studied using this technique [47][48][49][50].…”

Section: Advancements In Pnftmw Designmentioning

confidence: 99%

Towards a broadband chirped pulse Fourier transform microwave spectrometer

et al. 2012

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This article gives a brief review of microwave spectroscopy and the experimental techniques used for obtaining microwave spectrum of molecules and complexes since 1950s. It presents a brief summary of the pulsed nozzle Fourier transform microwave (PNFTMW) spectrometer, fabricated in our laboratory, and discusses some of the important results obtained using the spectrometer. The most significant among the results from this spectrometer is the direct structural determination of weakly bound complexes involving H 2 O/H 2 S. These have challenged the conventional wisdom on hydrogen bonding leading us to propose a modern definition for the same through IUPAC. The limitations of the PNFTMW spectrometer and the need for the new chirped pulse Fourier transform microwave spectrometer are discussed as well. Moreover, preliminary results from our laboratory on generating a 1 ls chirped pulse of 1 GHz bandwidth are given.

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Born-Oppenheimer breakdown effects and hyperfine structure in the rotational spectra of SbF and SbCl

Cited by 18 publications

References 51 publications

Theoretical study on molecular properties of SbX_n (X = F and Cl, n = 1–5) and SbX_n⁻ (X = F and Cl, n = 1–6) including spin–orbit coupling

Theoretical study on molecular properties of SbX_n (X = F and Cl, n = 1–5) and SbX_n⁻ (X = F and Cl, n = 1–6) including spin–orbit coupling

Fine and hyperfine structure of the transition of ND in vibrational excited states

Towards a broadband chirped pulse Fourier transform microwave spectrometer

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Born-Oppenheimer breakdown effects and hyperfine structure in the rotational spectra of SbF and SbCl

Cited by 18 publications

References 51 publications

Theoretical study on molecular properties of SbXn (X = F and Cl, n = 1–5) and SbXn− (X = F and Cl, n = 1–6) including spin–orbit coupling

Theoretical study on molecular properties of SbXn (X = F and Cl, n = 1–5) and SbXn− (X = F and Cl, n = 1–6) including spin–orbit coupling

Fine and hyperfine structure of the transition of ND in vibrational excited states

Towards a broadband chirped pulse Fourier transform microwave spectrometer

Contact Info

Product

Resources

About

Theoretical study on molecular properties of SbX_n (X = F and Cl, n = 1–5) and SbX_n⁻ (X = F and Cl, n = 1–6) including spin–orbit coupling

Theoretical study on molecular properties of SbX_n (X = F and Cl, n = 1–5) and SbX_n⁻ (X = F and Cl, n = 1–6) including spin–orbit coupling