Probing the Structure of CH<sub>5</sub><sup>+</sup> by Dissociative Charge Exchange

Mann, Jennifer E.; Xie, Zhen; Savee, John David; Braams, Bastiaan J.; Bowman, Joel M.; Continetti, Robert E.

doi:10.1021/ja0782504

Cited by 24 publications

(58 citation statements)

References 14 publications

(23 reference statements)

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“…Similar approaches were used previously describing other systems in which classical trajectories were initiated at geometries where electronic transitions to the ground electronic state occur. [22][23][24] This total energy corresponding to 4.46 eV relative to the OH͑r e ͒ +H 2 ͑r e ͒ asymptote, where "r e " denotes to the equilibrium bond length and is roughly the sum of the experimental energy 10 of 4.06 eV plus the sum of the OH and H 2 zero-point energies. ͓Hereafter all energies are given relative to OH͑r e ͒ +H 2 ͑r e ͒.͔ Trajectories were propagated on a new ground state adiabatic potential to determine the properties of the ground electronic state products.…”

Section: Introductionmentioning

confidence: 99%

Quasiclassical trajectory study of the postquenching dynamics of OH AΣ2+ by H2/D2 on a global potential energy surface

Kamarchik

Bowman

2010

The Journal of Chemical Physics

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We report full-dimensional, electronically adiabatic potential energy surfaces (PESs) for the ground state (1A(')) and excited state (2A(')) of OH(3). The PESs are permutationally invariant fits to roughly 23,000 electronic energies (MRCI + Q/aVTZ). Classical trajectory calculations of the postquenching dynamics of OH A (2)Σ(+) are carried out on the 1A(') PES for H(2) and D(2), at previously identified conical intersections (CoIs) [B. C. Hoffman and D. R. Yarkony, J. Chem. Phys. 113, 10091 (2000)]. The initial momenta are sampled fully and partially microcanonically, corresponding to "adiabatic" and "diabatic" models of the dynamics, respectively. Branching ratios of reactive to nonreactive channels from separate C(2v), C(∞v), and C(s) symmetries of CoIs are calculated, as are final rovibrational state distributions of OH and H(2) products. The rovibrational distributions of the OH and D(2) products, the D/H-atom translational energy distribution are calculated and compared to experimental ones. Agreement for these observable quantities is good. The branching between reactive and nonreactive quenching is sensitive to the momenta sampling; very good agreement with experiment is obtained using the diabatic sampling but not with the adiabatic sampling. The vibrational state distributions of H(2)O and HOD (although not measured by experiment) are also presented.

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Section: Introductionmentioning

confidence: 99%

Quasiclassical trajectory study of the postquenching dynamics of OH AΣ2+ by H2/D2 on a global potential energy surface

Kamarchik

Bowman

2010

The Journal of Chemical Physics

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“…However, most of these studies agreed in considering CH 5 + ion as a very fluxional species [63][64][65][66][67], whose basic components are a tripod CH 3 and a H 2 moiety. There are however some specific cases in which the coordination of carbon was found to be larger than four.…”

Section: Pentacovalent Carbon Atomsmentioning

confidence: 99%

Unexpected Gas-Phase Ion Chemistry Results Unraveled by Computational Chemistry

Gámez¹,

Corral²,

Mó³

et al. 2010

COC

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An overview of recent studies, which show the important role played by computational chemistry in explaining and predicting the behavior of a great variety of systems is presented. The first example illustrates the useful interplay experiment-theory which allowed to unambiguously characterize the X2(CH3)7 + (X = Si, Ge, Sn, Pb) cations as paradigmatic examples of molecular systems involving pentacovalently bound carbon atoms. Also, the possibility of deeply analyzing the bonding in molecular systems, led to a rationalization of the quite different behavior of acetylene and iminoborane derivatives, in spite of being isoelectronic species. Similarly, the analysis of the bonding perturbations usually associated with ion-molecule interactions in the gas phase, or with protonation and deprotonation processes, has made possible the characterization of non-conventional complexes as the key structures in the interactions of unsaturated and aromatic Si and Ge containing compounds with transition metal ions or to explain the dramatic enhanced acidity of alkylboranes and ,unsaturated borane derivatives.

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“…This exceeds the bond energy of H2O, but it is very likely that a large fraction of the energy is carried by fast H-atoms, leaving the H2O in bound states that are highly vibrationally excited. Recent experimental work by Mann et al (2008) on the dissociation of H3O following charge exchange of H3O + with Caesium revealed that H2O is produced in excited sym-metric/asymmetric stretch modes coupled with low bending and rotational excitation. The fact that the majority of the H3O + ions undergoing dissociative recombination were initially in ground vibrational states with a rotational temperature of 20-60 K and that the majority of the available energy is partitioned to H2O internal energy would appear to have direct parallels with vibrational excitation of H2O molecules initially in low J, ground vibrational states in the collisionally-dominated region of the cometary inner coma.…”

Section: Refmentioning

confidence: 99%

Water in the near-infrared spectrum of comet 8P/Tuttle

Barber¹,

Miller²,

Russo³

et al. 2009

Monthly Notices of the Royal Astronomical Society

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High-resolution spectra of comet 8P/Tuttle were obtained in the frequency range 3449.0-3462.2 cm −1 on 2008 January 3 UT using CGS4 with echelle grating on United Kingdom Infrared Telescope. In addition to observing solar pumped fluorescent lines of H 2 O, the long integration time (152 min on target) enabled eight weaker H 2 O features to be assigned, most of which had not previously been identified in cometary spectra. These transitions, which are from higher energy upper states, are similar in character to the so-called SH lines recorded in the post Deep Impact spectrum of comet Tempel 1. We have identified certain characteristics that these lines have in common, and which in addition to helping to define this new class of cometary line give some clues to the physical processes involved in their production. Finally, we derive an H 2 O rotational temperature of 62 ± 5 K and a water production rate of (1.4 ± 0.3) × 10 28 molecules s −1 .

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Probing the Structure of CH₅⁺ by Dissociative Charge Exchange

Cited by 24 publications

References 14 publications

Quasiclassical trajectory study of the postquenching dynamics of OH AΣ2+ by H2/D2 on a global potential energy surface

Quasiclassical trajectory study of the postquenching dynamics of OH AΣ2+ by H2/D2 on a global potential energy surface

Unexpected Gas-Phase Ion Chemistry Results Unraveled by Computational Chemistry

Water in the near-infrared spectrum of comet 8P/Tuttle

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Probing the Structure of CH5+ by Dissociative Charge Exchange

Cited by 24 publications

References 14 publications

Quasiclassical trajectory study of the postquenching dynamics of OH AΣ2+ by H2/D2 on a global potential energy surface

Quasiclassical trajectory study of the postquenching dynamics of OH AΣ2+ by H2/D2 on a global potential energy surface

Unexpected Gas-Phase Ion Chemistry Results Unraveled by Computational Chemistry

Water in the near-infrared spectrum of comet 8P/Tuttle

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Probing the Structure of CH₅⁺ by Dissociative Charge Exchange