High-Field Stark Effects on the Near Ultraviolet Spectrum of the Hydroxyl Radical

Scarl, Ethan A.; Dalby, F. W.

doi:10.1139/p71-340

Cited by 24 publications

(2 citation statements)

References 7 publications

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“…Only the vibration correction, 0.048 D, is large. Excitation amplitudes and the T 1 diagnostic are almost as small as for the ground state, yet the deviation from experiment 71 for the 2 Σ state is as large as 0.121 D. Unfortunately we were unable to find a more reliable experimental value (see also data from ref. 72 ).…”

Section: Oh Radical In the X 2 π Ground State And The A 2 σ + Excitedmentioning

confidence: 82%

Accuracy Assessment of the ROHF-CCSD(T) Calculationsof Dipole Moments of Small Radicals

Urban

Neogrády

Raab

et al. 1998

Collect. Czech. Chem. Commun.

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This paper is dedicated to Professor Rudolf Zahradnik on the occasion of his 70th birthday. One of us (M. U.) would never continued in his scientific work in theoretical chemistry without his help, advice and almost inexhaustible enthusiasm.Dipole moments of a series of radicals, OH, NO, NS, SF, SO, PO, ClO, CN, LiO, NO 2 , and ClO 2 were calculated by the Coupled Cluster CCSD(T) method with the single determinant restricted open shell Hartree-Fock (ROHF) reference. For all molecules theoretical dipole moments were carefully compared to experimental values. The size and the quality of the basis set were systematically improved. Spin adaptation in the ROHF-CCSD(T) method, largest single and double excitation amplitudes and the T 1 diagnostics were considered as indicators in the quality assessment of calculated dipole moments. For most molecules the accuracy within 0.01-0.03 D was readily obtained. For ClO and CN the spin adaptation was necessary -its contribution was as large as 0.03-0.045 D. Large deviation from experiment is observed for OH in its A 2 Σ + excited state (0.135 D) and especially for LiO in its 2 Π ground state (0.22 D). No indication of the failure of theoretical calculations was found which leads to the conclusion that, even if there is still a space for the improvement of theoretical calculations, experimental values should be reconsidered.

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Section: Oh Radical In the X 2 π Ground State And The A 2 σ + Excitedmentioning

confidence: 82%

Accuracy Assessment of the ROHF-CCSD(T) Calculationsof Dipole Moments of Small Radicals

Urban

Neogrády

Raab

et al. 1998

Collect. Czech. Chem. Commun.

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“…The OH distance of 0.972 Å is close to the experimental equilibrium value of 0.970. 33 The calculated dipole moment of 1.692 D compares with 1.721 ± 0.029, 34 and the fundamental mode is 5% higher than observed, 33 in which scaling by 0.956 35 causes a reduction to a 1% deviation.…”

Section: Resultsmentioning

confidence: 85%

Atmospheric Chemistry of Methyl Isocyanide–An Experimental and Theoretical Study

et al. 2020

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The reaction of CH 3 NC with OH radicals was studied in smog chamber experiments employing PTR-ToF-MS and long-path FTIR detection. The rate coefficient was determined to be k CH 3 NC+OH = (7.9 ± 0.6) × 10 –11 cm 3 molecule –1 s –1 at 298 ± 3 K and 1013 ± 10 hPa; methyl isocyanate was the sole observed product of the reaction. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ quantum chemistry calculations showing the reaction to proceed primarily via electrophilic addition to the isocyanide carbon atom. On the basis of the quantum chemical data, the kinetics of the OH reaction was simulated using a master equation model revealing the rate coefficient to be nearly independent of pressure at tropospheric conditions and having a negative temperature dependence with k OH = 4.2 × 10 –11 cm 3 molecule –1 s –1 at 298 K. Additional quantum chemistry calculations on the CH 3 NC reactions with O 3 and NO 3 show that these reactions are of little importance under atmospheric conditions. The atmospheric fate of methyl isocyanide is discussed.

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Sources of Error and Expected Accuracy in Ab Initio One‐Electron Operator Properties: The Molecular Dipole Moment

Green

1974

Advances in Chemical Physics

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High-Field Stark Effects on the Near Ultraviolet Spectrum of the Hydroxyl Radical

Cited by 24 publications

References 7 publications

Accuracy Assessment of the ROHF-CCSD(T) Calculationsof Dipole Moments of Small Radicals

Accuracy Assessment of the ROHF-CCSD(T) Calculationsof Dipole Moments of Small Radicals

Atmospheric Chemistry of Methyl Isocyanide–An Experimental and Theoretical Study

Sources of Error and Expected Accuracy in Ab Initio One‐Electron Operator Properties: The Molecular Dipole Moment

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