Study of vibrational interactions in DCO+ by millimeter-wave spectroscopy and determination of the equilibrium structure of the formyl ion

Dore, Luca; Beninati, Sabina; Puzzarini, Cristina; Cazzoli, G.

doi:10.1063/1.1564042

Cited by 26 publications

(21 citation statements)

References 20 publications

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“…H 2 : r H-H = 1.44875 bohrs (average over ground vibrational state); HCO + : r C-O = 2.0891 bohrs; and r H-C = 2.0634 bohrs, 24 neglecting the anharmonicity of the HC and OC bonds. Differences between equilibrium and average structure for HCO + are estimated to be less than 0.5%.…”

Section: A Ab Initio Computationsmentioning

confidence: 99%

The HCO+–H2 van der Waals interaction: Potential energy and scattering

Massó

Wiesenfeld

2014

The Journal of Chemical Physics

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We compute the rigid-body, four-dimensional interaction potential between HCO(+) and H2. The ab initio energies are obtained at the coupled-cluster single double triple level of theory, corrected for Basis Set Superposition Errors. The ab initio points are fit onto the spherical basis relevant for quantum scattering. We present elastic and rotationally inelastic coupled channels scattering between low lying rotational levels of HCO(+) and para-/ortho-H2. Results are compared with similar earlier computations with He or isotropic para-H2 as the projectile. Computations agree with earlier pressure broadening measurements.

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Section: A Ab Initio Computationsmentioning

confidence: 99%

The HCO+–H2 van der Waals interaction: Potential energy and scattering

Massó

Wiesenfeld

2014

The Journal of Chemical Physics

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“…As expected, equilibrium bond lengths optimized at the higher-order CCSD level are usually closest to the experimental values for the H 2 , CO, H 3 + , and HCO + molecules. [39][40][41] Our final geometries were determined at the CCSD/aug-cc-pVTZ level. Bending TSs for the isomerization reactions HOC + HCO + and H 2¯H OC + H 2¯H CO + were obtained at all three levels of theory.…”

Section: A Geometries and Energymentioning

confidence: 99%

Pathways and reduced-dimension five-dimensional potential energy surface for the reactions H3++CO→H2+HCO+ and H3++CO→H2+HOC+

Hirano

Roy

2008

The Journal of Chemical Physics

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To obtain theoretical insight regarding the stability and formation dynamics of the interstellar ions HCO(+) and HOC(+), stationary points and the associated vibrational frequencies on the full nine-dimensional potential energy surface for the electronic ground state have been calculated using coupled-cluster theory with both single and double substitutions (CCSD). The energetics were refined with a higher-level coupled-cluster method CCSD(T), with core-valence electron correlation treated at the complete basis set limit. To elucidate the formation mechanism and internal relaxation processes, the reaction paths for the reactions H(3) (+)+CO-->H(2)+HCO(+) and H(3) (+)+CO-->H(2)+HOC(+) were calculated at the second-order Moller-Plesset (MP2) level, and corresponding single-point energies were obtained at the higher CCSD(T)/aug-cc-pVTZ level. Based on the analysis of the main reaction processes, a reduced-dimension five-dimensional potential energy surface for this system was constructed from 128 440 ab initio points calculated at the CCSD(T)/aug-cc-pVTZ level.

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“…A centrifugal analysis extended to sextic terms could not account for such large residuals; in addition, this kind of anomaly is not present in the rotational spectrum of PHD 2 predicted from a set of centrifugal distortion parameters up to eighth order [25]. Therefore, a possible explanation might have been the occurrence of Stark shifts caused by the discharge electric field, as already observed in the analysis of ' doublets in bending excited states of DCO + [26]. This hypothesis, however, would imply an observation of a large broadening of the K " 0 transition lines of the symmetric species, due to the spreading of a M pattern induced by a first-order Stark effect.…”

Section: Experimental Details and Resultsmentioning

confidence: 76%