Roaming mediated nonadiabatic dynamics in molecular hydrogen elimination from propane at 157 nm

Rauta, Akshaya Kumar; Maiti, Biswajit

doi:10.1016/j.cplett.2016.08.057

Cited by 6 publications

(2 citation statements)

References 36 publications

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“…Typically, roaming takes place on a flat region of the potential energy surface, thus allowing nascent reaction products to remain near each other long enough for further reactions to occur. Of particular interest to the work presented, recent studies have focused on roaming processes in small organic molecules such as acetaldehyde 20 – 22 , acetone 23 , methyl formate 24 – 26 , and propane 27 . In most cases, the roaming pathway contributes a small fraction of the total yield.…”

Section: Introductionmentioning

confidence: 99%

H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields

et al. 2018

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Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here, the mechanistic details and femtosecond time-resolved dynamics of H3+ formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H2 roaming prior to H3+ formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H3+ formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H3+, the most important ion in interstellar chemistry, through H2 roaming occurring in ionic species.

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Section: Introductionmentioning

confidence: 99%

H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields

et al. 2018

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“…In this study, we have used trajectory surface-hopping (TSH) methodology as implemented in the NEWTON-X package . This methodology is similar to one used previously by our group to study the photodissociation of propyne and propane. , In brief, the potential energies, energy gradients, and nonadiabatic couplings are calculated using the COLUMBUS electronic structure program interfaced with NEWTON-X for integrating trajectories. Initially, the molecule is excited to the first singlet (S 1 ) state.…”

Section: Electronic Structure and Computational Detailsmentioning

confidence: 99%

Photodissociation Dynamics of Methyl Hydroperoxide at 193 nm: A Trajectory Surface-Hopping Study

Mahata

Maiti

2021

J. Phys. Chem. A

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The photodissociation of methyl hydroperoxide (CH3OOH) at 193 nm has been studied using a direct dynamics trajectory surface-hopping (TSH) method. The potential energies, energy gradients, and nonadiabatic couplings are calculated on the fly at the MRCIS(6,7)/aug-cc-pVDZ level of theory. The hopping of a trajectory from one electronic state to another is decided on the basis of Tully’s fewest switches algorithm. An analysis of the trajectories reveals that the cleavage of the weakest O–O bond leads to major products CH3O(2E) + OH(2Π), contributing about 72.7% of the overall product formation. This OH elimination was completed in the ground degenerate product state where both the ground singlet (S0) and first excited singlet (S1) states become degenerate. The O–H bond dissociation of CH3OOH is a minor channel contributing about 27.3% to product formation, resulting in products CH3OO + H. An inspection of the trajectories indicates that unlike the major channel OH elimination, the H-atom elimination channel makes a significant contribution (∼3% of the overall product formation) through the nonadiabatic pathway via conical intersection S1/S0 leading to ground-state products CH3OO(X 2A″) + H(2S) in addition to adiabatic dissociation in the first excited singlet state, S1, correlating to products CH3OO(1 2A′) + H(2S). The computed translational energy of the majority of the OH products is found to be high, distributed in the range of 70 to 100 kcal/mol, indicating that the dissociation takes place on a strong repulsive potential energy surface. This finding is consistent with the nature of the experimentally derived translational energy distribution of OH with an average translational energy of 67 kcal/mol after the excitation of CH3OOH at 193 nm.

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Analysis of the roaming trajectories from the dynamic and kinematic perspectives – A representative study of triatomic systems

Wang

Zheng

Yang

2021

Chemical Physics Letters

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Roaming mediated nonadiabatic dynamics in molecular hydrogen elimination from propane at 157 nm

Cited by 6 publications

References 36 publications

H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields

H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields

Photodissociation Dynamics of Methyl Hydroperoxide at 193 nm: A Trajectory Surface-Hopping Study

Analysis of the roaming trajectories from the dynamic and kinematic perspectives – A representative study of triatomic systems

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