The Ionization of Alkanes

Bouma, Willem J.; Poppinger, Dieter; Radom, Leo

doi:10.1002/ijch.198300004

Cited by 100 publications

(81 citation statements)

References 102 publications

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“…The distance between two H atoms bound to the same carbon atom is about 1.8 A and for that bond to different carbon atoms 2.1 A for both neutral ethane molecules and its ions. 23 We do not find vibrational excitation of H2*+ to the extent of that found with methane. Therefore, the ethane ion changed its geometry dramatically before H2'+ is lost, representative for a late barrier.…”

Section: Discussioncontrasting

confidence: 62%

Hydrogen (H2.bul.+) loss from methane and ethane under electron impact: an experimental study of transition-state geometries

Beijersbergen¹,

Zande²,

Kistemaker³

et al. 1993

J. Phys. Chem.

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Dissociative electron impact ionization of methane and ethane is studied by probing the nascent rovibrational distributions of the Hz'+ product ions. The H~'+(v, N) distribution is obtained by determining the kinetic energy release distribution of dissociating Hz*(v',N') molecules formed in neutralization of H 2 ' + ions on cesium atoms. Methane yields rotationally hot H2'+ ions (T = 10000 K) with a flat vibrational population distribution up to v = 6. Ethane yields rotationally colder Hz'+ ions ( T = 1700 K) with a broad vibrational population distribution that peaks at v = 0. In the case of methane the high rotational temperature reflects an asymmetric transition state, Le., an asynchronous stretching of the two C-H bonds. For ethane a more symmetric transition state is involved.

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Section: Discussioncontrasting

confidence: 62%

Hydrogen (H2.bul.+) loss from methane and ethane under electron impact: an experimental study of transition-state geometries

Beijersbergen¹,

Zande²,

Kistemaker³

et al. 1993

J. Phys. Chem.

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“…Electron correlation was taken into account within the PNO-CI (PNO stands for pseudonatural orbitals) method by Meyer, 7 and it has been predicted that a C 2v structure is the most stable geometry. Bouma et al 9 have supported this result by performing ab initio calculations at the MP2/6-31G* level.…”

Section: Introductionmentioning

confidence: 78%

Interconversion behavior of the CH bond in the CH radical cation: Ab initio molecular dynamics study

Ohta

Ohta²

2004

J Comput Chem

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Thermal motion of CH4+ is investigated by performing an ab initio molecular dynamics method with the second-order Møller-Plesset (MP2)/6-311G** force field. In the trajectories obtained at 400 K, we have observed rapid interconversion behavior of the geometrical parameters of CH4+ with the frequency of 0.6/ps, where the C-H pair forming the small angle around 55 degrees is switched to another pair on subpicosecond time scale. The switching patterns are found to be classified into the following two types. Type 1: one C-H of the small angled C-H pair is switched to one C-H of the other C-H pair. Type 2: the small angled C-H pair is switched to the other C-H pair, which has been newly observed in the present ab initio MD calculation. The four C-H bonds of CH4+ are characterized by the long and short C-H bonds in a time region of the trajectories, and also for the time-evolution of C-H bonds such interconversion behavior is observed. The switching patterns of the geometrical parameters are compared with those in the interconversion scheme between six equivalent C2v symmetry structures of CH4+ [Paddon-Row, M. N. et al., J Am Chem Soc 1985, 107, 7696]. We have also investigated the electronic energy fluctuation due to thermal motion of CH4+. The standard deviation of total electronic energy at 400 K is evaluated to be 1.2 kcal/mol.

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“…In cyclobutane, the planar rhomboid structure has previously been shown to lie lower in energy than any other planar conformation (~~2 / 6 -3 1 6 / / 3 -2 1~ calculations) [57]. On the other angle, where X is the midpoint between the two C' carbons) is 162.7".…”

Section: Cyclic Systemsmentioning

confidence: 94%

The effects of nonlocal gradient corrections in density functional calculations of hydrocarbon radical hyperfine structures

Eriksson

Malkin

Malkina

et al. 1994

Int J of Quantum Chemistry

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Ground-state equilibrium geometries and hyperfine structures of a number of organic neutral and charged radical compounds are computed using the linear combination of Gaussian-type orbitals-density functional theory method. In addition to the local spin-density approximation, we also use two different nonlocal (gradient corrected) schemes for the calculations of the exchange and correlation potentials. The different functional forms are found to generate slightly different total and unpaired spin-density distributions in the molecules, and as a result, the computed isotropic hyperfine coupling constants vary markedly. The smallest variations are found for the hydrogens, where the results are generally in satisfactory agreement with experiment. For the carbon atoms, however, large differences in isotropic coupling constants are observed. The anisotropic hyperfine structures are generally very well described at all levels of theory.

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The Ionization of Alkanes

Cited by 100 publications

References 102 publications

Hydrogen (H2.bul.+) loss from methane and ethane under electron impact: an experimental study of transition-state geometries

Hydrogen (H2.bul.+) loss from methane and ethane under electron impact: an experimental study of transition-state geometries

Interconversion behavior of the CH bond in the CH radical cation: Ab initio molecular dynamics study

The effects of nonlocal gradient corrections in density functional calculations of hydrocarbon radical hyperfine structures

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