Theoretical studies on bimolecular reaction dynamics

Clary, David C.

doi:10.1073/pnas.0800088105

Cited by 54 publications

(46 citation statements)

References 49 publications

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“…he AϩBC type reactions have long served as benchmarks in the development of the kinetics and dynamics theories of chemical reactions (1)(2)(3)(4)(5). However, behavior of polyatomic reactions may be qualitatively different from what has been deduced from studies of atom-diatom dynamics.…”

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confidence: 99%

Quasiclassical trajectory study of H+SiH ₄ reactions in full-dimensionality reveals atomic-level mechanisms

Cao

Zhang

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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potential energy surface ͉ reaction dynamics T he AϩBC type reactions have long served as benchmarks in the development of the kinetics and dynamics theories of chemical reactions (1-5). However, behavior of polyatomic reactions may be qualitatively different from what has been deduced from studies of atom-diatom dynamics. For example, a major reaction path, which does not follow the intrinsic reaction coordinate, has recently been found by Hase et al. (6) in their quasiclassical trajectory (QCT) study on the F Ϫ ϩCH 3 OOH reaction. Another example is the reaction of HϩCH 4 (and its isotopic variants), for which recent investigations (7) have focused on the new stripping mechanism observed by Zare and coworkers (8-9). The rebound mechanism is well-known for the HϩD 2 reaction (10-11), and a lot of polyatomic H abstraction reactions, including HϩCD 4 , have long been considered to proceed through this mechanism. However, in the recent combined experimental and theoretical studies on the reaction of HϩCD 4 (9, 12), the stripping mechanism was proposed, in which the velocity of incoming H atom is perpendicular to the C-D bond and the HD product is carried into the forward hemisphere. The stripping mechanism was further confirmed by Bowman and coworkers (13) using the QCT method.The HϩSiH 4 reaction is an analogue to HϩCH 4 , and both abstraction and exchange reactions can happen; i.e., Unlike the HϩCH 4 abstraction reaction, which is nearly thermoneutral, the HϩSiH 4 abstraction reaction R1 is exothermic by Ϸ13 kcal/mol, and regarded as a prototype of exothermic polyatomic H abstraction reactions. Also, as we will demonstrate, both reactions 1 (R1) and 2 (R2) could happen at collision energies above Ϸ12.5 kcal/mol, therefore the HϩSiH 4 reaction is actually a better candidate for studying the competition between abstraction and exchange than HϩCH 4 , for which the exchange channel is not open at collision energies Ͻ35 kcal/mol (noninversion exchange not open at Ͻ60 kcal/mol) (14). AbstractionIn this work, a global 12-dimensional potential energy surface (PES) that describes both abstraction and exchange reactions for the SiH 5 system is constructed, and detailed QCT calculations for both reactions R1 and R2 on this ab initio PES are performed, which yield insights into the reaction mechanism. The computed product angular distributions indicate that the abstraction reaction is a combination of rebound and stripping. More importantly, here we propose that the HϩSiH 4 exchange reaction is a combination of three mechanisms, inversion, torsion (more exactly, torsion-tilt), and side-inversion as demonstrated in Fig. 1. The interesting dynamical features for exchange can be explained with these atomic-level mechanisms. These findings are helpful for our understanding of the nature of polyatomic reactions, which goes beyond the atom-diatom pictures, and would have implications for a number of fields ranging from fundamental reaction dynamics to atmospheric and organic chemistry.The HϩSiH 4 reaction is important in the the...

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confidence: 99%

Quasiclassical trajectory study of H+SiH ₄ reactions in full-dimensionality reveals atomic-level mechanisms

Cao

Zhang

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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“…[1][2][3][4][5][6][7][8][9] In addition, the last few years has seen similar progress in predicting and explaining the detailed reaction mechanisms, selectivity, and activity of organometallic reactions in solvents that have guided experiment and been conrmed by experiment. [10][11][12][13] There has also been signicant progress in explaining key aspects of heterogeneous catalysts that have helped somewhat with guiding experiment with some conrmation from experiment.…”

Section: Introductionmentioning

confidence: 99%

Initial decomposition reaction of di-tetrazine-tetroxide (DTTO) from quantum molecular dynamics: implications for a promising energetic material

Goddard

et al. 2015

J. Mater. Chem. A

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Di-tetrazine-tetroxide (DTTO) was predicted in 2001 to have a density (up to 2.3 g cm À3) and heat of detonation (up to 421.0 kcal mol À1) better than other explosives, making it the "holy grail" of energetic materials (EMs), but all attempts at synthesis have failed. We report Density Functional Theory (DFT) molecular dynamics simulations (DFT-MD) on DTTO crystal for the two most stable monomers. We predict that the most stable isomer (c1) has a density of r ¼ ), a unique initial reaction among EMs. These results suggest that DTTO may have a higher thermal stability (barrier >7.0 kcal mol À1 higher) than RDX, HMX, and CL-20.

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“…1 is a sketch of the reaction coordinate for CH 3 D that shows the two reaction channels along with the vibrational levels of the reactant and of the two different methyl radical products, CH 3 and CH 2 D. The former comes from abstraction of the D atom and the latter from abstraction of one of the H atoms with the corresponding formation of DCl or HCl, respectively.…”

Section: Gas Phase Dynamics: Bimolecular Reactions Of Methane With Chmentioning

confidence: 99%

“…The additional possibility of using laser excitation to prepare reactants in individual quantum states and laser spectroscopic techniques to identify the final states of the products has produced a rich history of experimental studies that connect with comparably detailed theoretical descriptions (1,2). The interplay of theory and experiment in chemical reaction dynamics incisively tests models and calculations (3), and theory and experiment together often yield robust descriptions of chemical reactions at the most fundamental level.…”

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confidence: 99%

Chemical dynamics of vibrationally excited molecules: Controlling reactions in gases and on surfaces

Crim

2008

Proc. Natl. Acad. Sci. U.S.A.

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141

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Theoretical studies on bimolecular reaction dynamics

Cited by 54 publications

References 49 publications

Quasiclassical trajectory study of H+SiH ₄ reactions in full-dimensionality reveals atomic-level mechanisms

Quasiclassical trajectory study of H+SiH ₄ reactions in full-dimensionality reveals atomic-level mechanisms

Initial decomposition reaction of di-tetrazine-tetroxide (DTTO) from quantum molecular dynamics: implications for a promising energetic material

Chemical dynamics of vibrationally excited molecules: Controlling reactions in gases and on surfaces

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Theoretical studies on bimolecular reaction dynamics

Cited by 54 publications

References 49 publications

Quasiclassical trajectory study of H+SiH 4 reactions in full-dimensionality reveals atomic-level mechanisms

Quasiclassical trajectory study of H+SiH 4 reactions in full-dimensionality reveals atomic-level mechanisms

Initial decomposition reaction of di-tetrazine-tetroxide (DTTO) from quantum molecular dynamics: implications for a promising energetic material

Chemical dynamics of vibrationally excited molecules: Controlling reactions in gases and on surfaces

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Quasiclassical trajectory study of H+SiH ₄ reactions in full-dimensionality reveals atomic-level mechanisms

Quasiclassical trajectory study of H+SiH ₄ reactions in full-dimensionality reveals atomic-level mechanisms