Dynamics of the O( 3 P, 1 D) + SiH 4 reaction: A trajectory surface hopping study

Ghosh, Subhendu; Mandal, Mrinmoy; Maiti, Biswajit

doi:10.1016/j.cplett.2017.10.040

Cited by 5 publications

(10 citation statements)

References 35 publications

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“…6) with a peak in the 7–8 kcal mol −1 zone. This result agrees with a previous theoretical study 21 and with the experimental evidence. 20 Fig.…”

Section: Dynamics Results and Discussionsupporting

confidence: 94%

“…In this section we performed the dynamics study at a collision energy of 8.0 kcal mol −1 , to compare with the experiments by Lin et al 20 and previous theoretical studies by Ghosh et al , 21 who reported only the translational and angular distributions. At this energy the reactivity of this reaction is higher than at room temperature.…”

Section: Dynamics Results and Discussionmentioning

confidence: 91%

“…In these studies, an added problem is that the role of the oxygen electronic state, O( 3 P), ground state, and O( 1 D), excited state, reactions with silane is not clear at this moment, 20 and very few dynamics studies have been reported, either experimentally 5,6,20 or theoretically. 15,21 From previous literature [5][6][7]15,20,21 there is a consensus that while the O( 1 D) + SiH 4 -Products reaction evolves through an insertion/addition mechanism with a very stabilized complex in the entrance channel and a barrierless process, the O( 3 P) + SiH 4 -Products reaction evolves through a direct hydrogen abstraction reaction with a noticeable barrier height. The rate constants for the O( 1 D) + SiH 4 reaction, then, are significantly higher than for the O( 3 P) + SiH 4 reaction.…”

Section: Introductionmentioning

confidence: 99%

“…For this reason, we draw attention to the theory/experiment comparison throughout this paper. (v) Finally, although previous theoretical studies 10,15,16,21 have analysed this reaction using different methods, to the best of our knowledge an analytical fulldimensional potential energy surface (PES) describing the nuclei motion within the Born-Oppenheimer approximation, has not been reported.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Theoretical study of the O(³P) + SiH₄ reaction: global potential energy surface, kinetics and dynamics study

Rangel

Espinosa‐García

2022

Phys. Chem. Chem. Phys.

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“…6) with a peak in the 7–8 kcal mol −1 zone. This result agrees with a previous theoretical study 21 and with the experimental evidence. 20 Fig.…”

Section: Dynamics Results and Discussionsupporting

confidence: 94%

Section: Dynamics Results and Discussionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Theoretical study of the O(³P) + SiH₄ reaction: global potential energy surface, kinetics and dynamics study

Rangel

Espinosa‐García

2022

Phys. Chem. Chem. Phys.

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“…We have computed spin–orbit coupling (SOC) matrix elements at each time step of a trajectory to calculate hopping probability between the triplet and singlet states by interfacing our dynamics code with GAMESS suits of program . The spin–orbit coupling calculation scheme is similar to that reported by Ghosh et al For completeness, however, we summarize the procedure in brief. The molecular orbitals (MOs) were generated from a four-state state-averaged CASSCF(6,6) calculation using an aug-cc-pVDZ basis set.…”

Section: Electronic Structure and Direct Dynamics Calculationsmentioning

confidence: 99%

Dynamics of the C(³P) + Ethylene Reaction: A Trajectory Surface Hopping Study

2018

Self Cite

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The direct dynamics trajectory surface hopping (DDTSH) method has been employed to study the reaction of C(P) with ethylene (CH). Our trajectory simulations show that at a reagent collision energy of 7.36 kcal/mol, there are two possible product channels: propargyl (HCCCH) + H and carbene (CH) + acetylene (HCCH). Estimated branching ratios based on trajectory propagations indicate that propargyl radical formation is the dominant channel contributing (94.1 ± 5.2) % of the overall products formation with (5.9 ± 1.7)% contribution from the minor CH + HCCH channel. These findings are consistent with earlier experimental observations and theoretical predictions that propargyl (HCCCH) formation is the dominant channel for the C(P) + CH collision reaction. Our trajectory simulations, however, unravel five distinctly different dynamical pathways, unlike earlier experimental and theoretical predictions of only two pathways proposed for the formation of propargyl radical, and three different dynamics are followed for the CH + HCCH channel (this channel was not detected experimentally). The computed translational energy distribution for the propargyl + H channel is narrower and showed peak maximum at a lower energy compared to the experimental one. While the center of mass product angular distribution based on our trajectory propagation is nearly isotropic in nature indicating formation of long-lived intermediate complexes, the experimental one was reported to be backward-forward distributed with more intensity in the forward direction indicating the formation of an osculating complex. Our trajectory surface hopping calculations confirm that the effect of intersystem crossing (ISC) is not important for the title reaction presumably because of weak spin-orbit coupling values (<10 cm) for the (C + CH) system. No trace of cyclic products formation was obtained from our trajectory simulations, which however was predicted to be a minor (2%) product channel, experimentally.

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Exploring unimolecular reactions in disilanol and ethanol: Insights and challenges

Vázquez,

Martínez-Núñez,

Preston

2023

Theor Chem Acc

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Unimolecular reactions of small silicon oxyhydrides constitute a subset of the full reaction networks that lead to larger species. Previous methods for mechanism discovery have largely been done by manual exploration using chemical intuition. Those works have established general concepts for silanol, SiOH4. The present work is a first attempt to use the automated mechanism discovery of the program AutoMeKin to elucidate the unimolecular reactions of disilanol, Si2OH6. We find that the semi-empirical surfaces used for preliminary exploration insufficiently describe silicon chemistry. As a workaround, we implement an intermediate optimization step to temper these shortcomings. The method recovers the known mechanisms in SiOH4 and C2OH6, which we use for validation. Key results for Si2OH6 include descriptions of relevant elementary reactions, the reaction network, and comparisons with better-known hydrocarbon and silicon hydride reactions. Although the current method shows promise, some shortcomings arise. We discuss the reliability of the generated reaction network and address approaches for further mechanistic understanding of silicon chemistry for material synthesis.

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Dynamics of the O( 3 P, 1 D) + SiH 4 reaction: A trajectory surface hopping study

Cited by 5 publications

References 35 publications

Theoretical study of the O(³P) + SiH₄ reaction: global potential energy surface, kinetics and dynamics study

Theoretical study of the O(³P) + SiH₄ reaction: global potential energy surface, kinetics and dynamics study

Dynamics of the C(³P) + Ethylene Reaction: A Trajectory Surface Hopping Study

Exploring unimolecular reactions in disilanol and ethanol: Insights and challenges

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Dynamics of the O( 3 P, 1 D) + SiH 4 reaction: A trajectory surface hopping study

Cited by 5 publications

References 35 publications

Theoretical study of the O(3P) + SiH4 reaction: global potential energy surface, kinetics and dynamics study

Theoretical study of the O(3P) + SiH4 reaction: global potential energy surface, kinetics and dynamics study

Dynamics of the C(3P) + Ethylene Reaction: A Trajectory Surface Hopping Study

Exploring unimolecular reactions in disilanol and ethanol: Insights and challenges

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Theoretical study of the O(³P) + SiH₄ reaction: global potential energy surface, kinetics and dynamics study

Theoretical study of the O(³P) + SiH₄ reaction: global potential energy surface, kinetics and dynamics study

Dynamics of the C(³P) + Ethylene Reaction: A Trajectory Surface Hopping Study