Infrared diode laser spectroscopic investigation of four C–H stretching vibrational modes of propylene oxide

Sunahori, Fumie X.; Su, Zheng; Kang, Cheolhwa; Xu, Yunjie

doi:10.1016/j.cplett.2010.05.072

Cited by 11 publications

(6 citation statements)

References 47 publications

(70 reference statements)

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“…The maximum (|MAX|) and mean (MAE) absolute errors, as well as the maximum relative error weighted by the reference value (|REL|, given in %) are reported with respect to experimental data from (Mellouki et al, 2001 ) and intensities (km/mol) for the first 18 modes (by increasing energy) of methyloxirane computed at the B3PW91/SNSD and hybrid revDSD-PBEP86-D3(BJ)/jun-cc-pVTZ//B3PW91/SNSD levels of theory and with different VPT2 schemes. The maximum (|MAX|) and mean (MAE) absolute errors, as well as the maximum relative error weighted by the reference value (|REL|, given in %) are reported with respect to experimental data from (Polavarapu et al, 1985;Sunahori et al, 2010;Merten et al, 2013 compared to 18 and 34). However, the behavior is not consistent and the distribution of errors differs between the two levels of electronic structure calculation methods.…”

Section: Furan and Methyloxiranementioning

confidence: 99%

Accuracy and Reliability in the Simulation of Vibrational Spectra: A Comprehensive Benchmark of Energies and Intensities Issuing From Generalized Vibrational Perturbation Theory to Second Order (GVPT2)

Yang

Mendolicchio

Barone

et al. 2021

Front. Astron. Space Sci.

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Vibrational spectroscopy represents an active frontier for the identification and characterization of molecular species in the context of astrochemistry and astrobiology. As new missions will provide more data over broader ranges and at higher resolution, especially in the infrared region, which could be complemented with new spectrometers in the future, support from laboratory experiments and theory is crucial. In particular, computational spectroscopy is playing an increasing role in deepening our understanding of the origin and nature of the observed bands in extreme conditions characterizing the interstellar medium or some planetary atmospheres, not easily reproducible on Earth. In this connection, the best compromise between reliability, feasibility and ease of interpretation is still a matter of concern due to the interplay of several factors in determining the final spectral outcome, with larger molecular systems and non-covalent complexes further exacerbating the dichotomy between accuracy and computational cost. In this context, second-order vibrational perturbation theory (VPT2) together with density functional theory (DFT) has become particularly appealing. The well-known problem of the reliability of exchange-correlation functionals, coupled with the treatment of resonances in VPT2, represents a challenge for the determination of standardized or “black-box” protocols, despite successful examples in the literature. With the aim of getting a clear picture of the achievable accuracy and reliability of DFT-based VPT2 calculations, a multi-step study will be carried out here. Beyond the definition of the functional, the impact of the basis set and the influence of the resonance treatment in VPT2 will be analyzed. For a better understanding of the computational aspects and the results, a short summary of vibrational perturbation theory and the overall treatment of resonances for both energies and intensities will be given. The first part of the benchmark will focus on small molecules, for which very accurate experimental and theoretical data are available, to investigate electronic structure calculation methods. Beyond the reliability of energies, widely used for such systems, the issue of intensities will also be investigated in detail. The best performing electronic structure methods will then be used to treat larger molecular systems, with more complex topologies and resonance patterns.

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Section: Furan and Methyloxiranementioning

confidence: 99%

Accuracy and Reliability in the Simulation of Vibrational Spectra: A Comprehensive Benchmark of Energies and Intensities Issuing From Generalized Vibrational Perturbation Theory to Second Order (GVPT2)

Yang

Mendolicchio

Barone

et al. 2021

Front. Astron. Space Sci.

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“…The 2900-3100 cm −1 wavenumbers range: high-resolution jet-cooled IR spectrum from Ref. 106 . The 200-1600 cm −1 wavenumbers range: low-temperature matrix data from Refs.…”

Section: Figmentioning

confidence: 99%

Accurate molecular structures and infrared spectra of trans-2,3-dideuterooxirane, methyloxirane, and trans-2,3-dimethyloxirane

Barone

Biczysko

Bloino

et al. 2014

The Journal of Chemical Physics

147

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Oxirane derivatives are the most used benchmarks for chiroptical spectroscopies in view of their small size and relative rigidity. The molecular structure, vibrational harmonic and anharmonic frequencies, and infrared intensities of the ground electronic states are analyzed in this paper. Equilibrium structure and harmonic force fields have been evaluated by means of high-level quantum-chemical calculations at the coupled-cluster level including single and double excitations together with a perturbative treatment of triples (CCSD(T)). Extrapolation to the complete basisset limit as well as core-correlation effects have also been taken into account. Anharmonic contributions have been computed at the CCSD(T)/cc-pVTZ level for trans-2,3-dideuterooxirane. These data can serve as references to evaluate the accuracy of less expensive computational approaches rooted in the density functional theory (DFT). The latter have been used within hybrid CC/DFT approaches, which have been applied to simulate fully anharmonic infrared (IR) spectra. Finally, the best theoretical estimates of the equilibrium structures and vibrational wavenumbers are compared to the most accurate experimental data and show in all cases very good agreement, i.e., within 0.001 Å, 0.1 degrees and 10 cm −1 and 0.5 km mol −1 , for bond lengths, angles, wavenumbers and IR intensities, respectively.

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“…For example, in rare gas-PO [19][20][21][22] and CO 2 -PO, [23] the rare gas atoms and CO 2 prefer to stay at the antiposition, i. e. opposite from the CH 3 group, whereas in the mono-and dihydrates of PO, water prefers to stay in the synposition. [24,25] In addition, rotational spectra of several PO containing homo-/heterochiral dimers [19,[26][27][28][29][30] and even the PO trimer [31] were analyzed, uncovering the complex conforma-tional panorama and rich structural diversity associated with these binary and ternary chiral clusters.…”

Section: Introductionmentioning

confidence: 99%

Conformational Landscape, Chirality Recognition and Chiral Analyses: Rotational Spectroscopy of Tetrahydro‐2‐Furoic Acid⋅⋅⋅Propylene Oxide Conformers

et al. 2021

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A chiral adduct formed between a chiral carboxylic acid, tetrahydro‐2‐furoic acid (THFA), and a chiral ester, propylene oxide (PO), was investigated using rotational spectroscopy and DFT calculations. Isolated THFA exists dominantly as three different conformers: I, II, and III in a jet, with I and II taking on the trans‐COOH configuration and III having the cis‐COOH configuration. We utilized CREST, a conformational ensemble space exploration tool, to identify the possible conformations of the binary adduct, THFA⋅⋅⋅PO. Subsequent DFT geometry optimizations predicted about two hundred homochiral and heterochiral binary structures with 28 low energy structures within an energy window of 15 kJ mol−1. A rich broadband rotational spectrum was obtained with a mixture of trace amounts of THFA+PO in neon in a supersonic jet expansion. Six THFA⋅⋅⋅PO conformers were identified experimentally. Kinetically favored binary products which contain trans‐COOH I dominate among the observed conformers, while thermodynamically more stable adducts were also detected. Detailed analyses of the structures of the observed conformers show interesting chirality‐controlled structural preferences. Such non‐covalently bound chiral contact pairs are the foundation of chiral‐tag rotational spectroscopy, an exciting new analytical application of rotational spectroscopy for determination of enantiomeric excess. Enantiomeric excess analyses were performed and the results are discussed.

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Infrared diode laser spectroscopic investigation of four C–H stretching vibrational modes of propylene oxide

Cited by 11 publications

References 47 publications

Accuracy and Reliability in the Simulation of Vibrational Spectra: A Comprehensive Benchmark of Energies and Intensities Issuing From Generalized Vibrational Perturbation Theory to Second Order (GVPT2)

Accuracy and Reliability in the Simulation of Vibrational Spectra: A Comprehensive Benchmark of Energies and Intensities Issuing From Generalized Vibrational Perturbation Theory to Second Order (GVPT2)

Accurate molecular structures and infrared spectra of trans-2,3-dideuterooxirane, methyloxirane, and trans-2,3-dimethyloxirane

Conformational Landscape, Chirality Recognition and Chiral Analyses: Rotational Spectroscopy of Tetrahydro‐2‐Furoic Acid⋅⋅⋅Propylene Oxide Conformers

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