The dissociative ionization of carbon dioxide below 21.22eV. A high resolution PIPECO spectroscopic investigation

Locht, Robert

doi:10.1016/0168-1176(95)04289-w

Cited by 12 publications

(15 citation statements)

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“…67 This study focused primarily on understanding the energetics of the non-dissociative charge-transfer process and revealed the presence of excited states of CO 2 2+ in the reactant beam, in addition to the ground 3 2+ capturing an electron. 9,14,18,19,23,24,26 4.1.1 The dissociation of CO 2 + ions. In the CO 2 2+ /CO 2 collision system (Table 1) the energy released by the reaction of a ground state dication with CO 2 to form a pair of CO 2 + ions in their ground states is 9.8 eV.…”

Section: Discussionmentioning

confidence: 99%

“…The dissociation of carbon dioxide monocations with internal energies in this range has been extensively investigated. Greatest attention 9,14,18,19,23,24,26 has focussed on the population and dissociation of the C 2 S + g state of CO 2 + which lies 5.6 eV above the ground state of CO 2 + . In addition, the dissociation of the higher lying (8.8 eV) 2 2 P u state of CO 2 + has also been considered.…”

Section: Discussionmentioning

confidence: 99%

“…As for many small molecules, the single ionisation of carbon dioxide (CO 2 ) has been extensively investigated via a wide variety of methodologies. [1][2][3][4][5][6][7][8][9][10][11][12][13] Similarly, the dissociation of CO 2 + has been extensively studied using photoionization, [14][15][16][17][18][19] electron ionisation, 20,21 coincidence 9,18,[22][23][24][25] and computational techniques. 9,26,27 There has also been increasing recent interest in the formation, dissociation and reactivity of CO 2 2+ , the carbon dioxide dication, [28][29][30][31][32][33][34][35] an interest further stimulated by the predicted presence of long-lived CO 2 2+ ions in the Martian atmosphere.…”

Section: Introductionmentioning

confidence: 99%

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Selective dissociation in dication–molecule reactions

Parkes

Lockyear

Price

et al. 2010

Phys. Chem. Chem. Phys.

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The single electron transfer reactions between (13)CO(2)(2+) and (12)CO(2) and between (18)O(2)(2+) and (16)O(2) have been studied, using a position-sensitive coincidence technique, to test recently proposed explanations for the preferential dissociation of the (13)CO(2)(+) ion (the capture monocation) formed following electron transfer to (13)CO(2)(2+). In our studies of the carbon dioxide collision system, in agreement with previous work, the capture monocation shows a greater propensity to dissociate than the monocation formed from the neutral, (12)CO(2)(+) (the ejection monocation). The coincidence data clearly show that the dissociation pathways of the (13)CO(2)(+) and (12)CO(2)(+) ions are different and are consistent with the ejection monocation dissociating via population of the C(2)Sigma state, whilst the capture ion is predominantly directly formed in dissociative quartet states. This state assignment is in accord with an expected preference for one-electron transitions in the electron transfer process. A propensity for one-electron transitions also rationalizes our observation that following dissociative single electron transfer between (18)O(2)(2+) and (16)O(2) the ejection monocation ((16)O(2)(+)) preferentially dissociates; the opposite situation to that observed for carbon dioxide. The coincidence results for this reaction indicate the (16)O(2)(+) dissociation results from population of the B((2)Sigma) state. The less favoured dissociation of the capture monocation clearly involves population of a different electronic state(s) to those populated in the ejection ion. Indeed, the experimental data are consistent with the dissociation of the capture monocation via predissociated levels of the b((4)Sigma) state. Since the population of the B((2)Sigma) state from the neutral O(2) molecule involves a one-electron transition, and the population of the valence dissociative states of O(2)(+) from the dication are multi-electron processes, the preferential dissociation of the ejection monocation in this collision system can be rationalized by the same principles used to explain the electron transfer reactivity of CO(2)(2+) with CO(2).

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Selective dissociation in dication–molecule reactions

Parkes

Lockyear

Price

et al. 2010

Phys. Chem. Chem. Phys.

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“…Here one may argue, however, that in a randomly aligned sample this effect would be unlikely to become dominant, so further reasons for the increased branching ratio should be considered. It might for example be possible that mainly the highest lying vibrational states (≥ 19.76 eV) were populated through collision excitation, as these have been shown to exclusively produce CO + (1,0) [233].…”

Section: Branching Ratiomentioning

confidence: 99%

“…It has been found that the C state fully predissociates and dominates the fragmentation mechanism. Several theoretical and experimental studies have thus been performed to understand the corresponding dissociation dynamics [15,230,232,233,[235][236][237]. Due to the dissociation limits of the respective fragments, O + (1,0) may be produced from its vibrational ground state, whereas CO + (1,0) can only result from vibrationally excited states.…”

Section: Predissociation Mechanismmentioning

confidence: 99%

Resolving Strong Field Dynamics in Cation States of CO_2 via Optimised Molecular Alignment

Oppermann

2014

Springer Theses

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In this thesis, the role of the molecular structure in strong field induced processes in CO 2 is resolved by the use of optimised impulsive molecular alignment. Two processes were investigated: recollision induced ionisation and the dissociation of the molecular ion CO + 2 . Both processes are driven by the initial tunneling ionisation of CO 2 . Through the use of molecular alignment, the orbital symmetries of the involved molecular ionic states were resolved, revealing the internal molecular dynamics in the form of ionisation and excitation pathways.A novel data analysis procedure was developed to extract the alignment distribution and rotational temperature of the impulsively aligned molecular ensemble. This facilitated the optimisation of molecular alignment in mixed gas samples and was demonstrated for N 2 , O 2 and CO 2 seeded in Ar.The recollision induced or nonsequential double ionisation (NSDI) of CO 2 was then studied in the molecular frame. The process was fully characterised by measuring the shape of the recolliding electron wavepacket and the angularly resolved inelastic electronion recollision cross section. The results reveal the contribution from both the ionic ground and first excited state of CO + 2 to the NSDI mechanism. This study was extended to the strong field induced dissociation of impulsively aligned CO + 2 . It was found that dissociation is driven by a parallel dipole transition from the second excited ionic state B to the predissociating state C, whilst recollision excitation was shown to not play a role. The strong field induced coupling of the ionic states B and C could thus be controlled by the laser polarisation.The results obtained in this thesis further the understanding of population dynamics of cation states in strong field processes. This is of special interest for extending molecular strong field physics to the study of electronic degrees of freedom and their coupling to the nuclear motion. had hoped for in a research degree and I cannot thank Jon enough for making it such an enriching experience, both professionally and personally.

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Strong Field Control of Dissociative Excitation in CO$$_2^+$$

Oppermann

2014

Resolving Strong Field Dynamics in Cation States of CO_2 via Optimised Molecular Alignment

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The dissociative ionization of carbon dioxide below 21.22eV. A high resolution PIPECO spectroscopic investigation

Cited by 12 publications

References 11 publications

Selective dissociation in dication–molecule reactions

Selective dissociation in dication–molecule reactions

Resolving Strong Field Dynamics in Cation States of CO_2 via Optimised Molecular Alignment

Strong Field Control of Dissociative Excitation in CO$$_2^+$$

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