Rovibrational spectrum and analysis of the ν8 band of thiophene using infrared synchrotron radiation

Wijngaarden, Jennifer van; Nest, Samantha J. Van; Dijk, Cody W. van; Tokaryk, D. W.

doi:10.1016/j.jms.2009.10.001

Cited by 7 publications

(3 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…From the c -coordinates in particular, it is evident that the ground-state geometry is closer to that of TS-I and TS-II (but slightly closer to that of TS-I) than to the equilibrium geometry of conformer I. To describe the geometry of thiophene–w in terms of the principal axis system of the thiophene monomer, a Kraitchman analysis was also performed, treating the water molecule (mass of 18.01056 amu) as a substitution site of the thiophene monomer. This provided substitution coordinates { a , b , c } with absolute values of 0.523(3), 0.267(6), and 3.3801(5) Å, which places the center of mass of water slightly out of the a – c plane (σ v ) of thiophene (0.267(6) Å), which would be analogous to the c -coordinate in the TS of the thiophene–w complex (Figure , top).…”

Section: Discussionmentioning

confidence: 99%

Characterization of Large-Amplitude Motions and Hydrogen Bonding Interactions in the Thiophene–Water Complex by Rotational Spectroscopy

Silva

Wijngaarden

2021

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

The rotational fingerprint of the thiophene–water complex was investigated for the first time using Fourier transform microwave spectroscopy (7–20 GHz) aided by quantum mechanical calculations. Transitions for a single species were observed, and the rotational constants for the parent and 18O isotopomers are consistent with a geometry that is highly averaged over a barrierless large-amplitude motion of water that interconverts two equivalent forms corresponding to the global minimum (B2PLYP-D3(BJ)/def2-TZVP). In this effective geometry, the water lies above the thiophene ring close to its σv plane of symmetry. The observed transitions are split by a second water-centered tunneling motion that exchanges its two protons by internal rotation about its C2 axis with a calculated barrier of ∼2.7 kJ mol–1 (B2PLYP-D3(BJ)/def2-TZVP). Based on quantum theory of atoms in molecules, noncovalent interaction, and symmetry-adapted perturbation theory analyses, the observed geometry enables two intermolecular interactions (O–H···π and O–H···S) whose electrostatic and dispersive contributions favor formation of the thiophene–water complex.

show abstract

Section: Discussionmentioning

confidence: 99%

Characterization of Large-Amplitude Motions and Hydrogen Bonding Interactions in the Thiophene–Water Complex by Rotational Spectroscopy

Silva

Wijngaarden

2021

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

show abstract

“…Vibrational transitions of the pyridyl radical have been recently measured by cryogenically cooled slow photoelectron velocity map imaging (cryo-SEVI) 67 and matrix isolation infrared spectroscopy. 68 Stable 5-membered heterocycles have been studied with rotational resolution using Fourier transform infrared spectroscopy with synchrotron sources (e.g., including pyrrole, 69 furan, 70 thiophene 71 ), and with an appropriate plasma source or F-abstraction technique, 72 the pyrrolyl radicals may be amenable to detection using these methods.…”

Section: Implications For Laboratory Spectroscopy and Astronomymentioning

confidence: 99%

Coupled Cluster Characterization of 1-, 2-, and 3-Pyrrolyl: Parameters for Vibrational and Rotational Spectroscopy

Johansen

Westerfield

et al. 2021

J. Phys. Chem. A

View full text Add to dashboard Cite

Pyrrolyl (C 4 H 4 N) is a nitrogen-containing aromatic radical that is a derivative of pyrrole (C 4 H 5 N) and is an important intermediate in the combustion of biomass. It is also relevant for chemistry in Titan's atmosphere and may be present in the interstellar medium. The lowest-energy isomer, 1-pyrrolyl, has been involved in many experimental and theoretical studies of the N -H photodissociation of pyrrole, yet it has only been directly spectroscopically detected via electron paramagnetic resonance and through the photoelectron spectrum of the pyrrolide anion, yielding three vibrational frequencies. No direct measurements of 2-or 3-pyrrolyl have been made, and little information is known from theoretical calculations beyond their relative energies. Here, we present an ab initio quantum chemical characterization of the three pyrrolyl isomers at the CCSD(T) level of theory in their ground electronic states, with an emphasis on spectroscopic parameters relevant for vibrational and rotational spectroscopy. Equilibrium geometries were optimized at the CCSD(T)/cc-pwCVTZ level of theory, and the quadratic, cubic, and partial quartic force constants were evaluated at CCSD(T)/ANO0 for analysis using second-order vibrational perturbation theory to obtain harmonic and anharmonic vibrational frequencies. In addition, zero-pointcorrected rotational constants, electronic spin-rotation tensors, and nuclear hyperfine tensors are calculated for rotational spectroscopy. Our computed structures and energies agree well with earlier density functional theory calculations, and spectroscopic parameters for 1-pyrrolyl are compared with the limited existing experimental data. Finally, we discuss strategies for detecting these radicals using rotational and vibrational spectroscopy on the basis of the calculated spectroscopic constants.

show abstract

“…Vibration-rotation bands of a number of organic ring molecules have been studied at CLS by Tokaryk, van Wijngaarden, and co-workers. These include thiophene [61,62], pyrrole [63], b-propiolactone [64], azetidine [65], and silacyclobutane (c-C 3 H 8 Si) [66]. This work and the closely related results from MAX-lab described above [45] illustrate how the scope of far-IR vibration-rotation spectroscopy has now expanded to include larger and heavier organic molecules whose spectra would previously have been too congested for analysis.…”

mentioning

confidence: 97%

High-resolution infrared spectroscopy with synchrotron sources

McKellar

2010

Journal of Molecular Spectroscopy

View full text Add to dashboard Cite

Rovibrational spectrum and analysis of the ν8 band of thiophene using infrared synchrotron radiation

Cited by 7 publications

References 17 publications

Characterization of Large-Amplitude Motions and Hydrogen Bonding Interactions in the Thiophene–Water Complex by Rotational Spectroscopy

Characterization of Large-Amplitude Motions and Hydrogen Bonding Interactions in the Thiophene–Water Complex by Rotational Spectroscopy

Coupled Cluster Characterization of 1-, 2-, and 3-Pyrrolyl: Parameters for Vibrational and Rotational Spectroscopy

High-resolution infrared spectroscopy with synchrotron sources

Contact Info

Product

Resources

About