Quantum dynamical study of the electronic nonadiabaticity in the D + DBr → Br(Br*) + D2 reaction on new diabatic potential energy surfaces

Zhang, Ai-Jie; Zhang, Peiyu; Chu, Tianshu; Han, Keli; He, Guo‐Zhong

doi:10.1063/1.4766355

Cited by 13 publications

(15 citation statements)

References 32 publications

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“…It is evident that the results change little with the neglect of the V 1 and V 2 , in other words, the spin-orbit coupling is primarily responsible for the electronic nonadiabaticity in the title reactions. Figure 7 is qualitatively similar to the earlier predictions of the H + HBr and D + DBr reaction [15]. In view of the fact that off-diagonal coupling potentials V 1 and V 2 are only 1−5% of the spin-orbit coupling, this result is reasonable.…”

Section: Resultssupporting

confidence: 85%

“…[15] and [20], we did not give an quantitative conclusion about the effect of isotopic effects on the electronic nonadiabaticity. As shown in Fig.…”

Section: Resultscontrasting

confidence: 49%

“…Han and coworkers [15] have reported the recent diabatic potential energy surfaces for the BrH 2 system. It is of interest to illustrate the characteristics of the ground PES which can contribute to expound the dynamical results in Section IV.…”

Section: Potential Energy Surfacesmentioning

confidence: 99%

“…Based on the dynamical calculations on JXX1 PES, Xie et al [14] found that the thermal rate constants were in good agreement with the experimental values in a wide range of temperatures for the H + HBr abstraction reaction. Very recently, Han et al [15] presented a new set of diabatic PESs for the BrH 2 system and carried out dynamical calculation for the D +DBr reaction. The obtained theoretical nonadiabatic effect and rate constant are in good agreement with experiments.…”

Section: Introductionmentioning

confidence: 99%

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Quantum dynamics study of H + DBr and D + HBr reaction

Zhang

Jia

et al. 2014

J Mol Model

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Time-dependent quantum wave packet calculations have been performed for the H + DBr and D + HBr reaction using the recent diabatic potential energy surfaces. Reaction probabilities, integral cross sections, and rate constants are obtained. The results show that the isotopic effects have an influence on the nonadiabatic effect which is generally inversely proportional to the atom mass. The calculated rate constants are in good overall agreement with experimental values, indicating that the ab initio surfaces are accurate to describe the isotopic effects.

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Section: Resultssupporting

confidence: 85%

“…[15] and [20], we did not give an quantitative conclusion about the effect of isotopic effects on the electronic nonadiabaticity. As shown in Fig.…”

Section: Resultscontrasting

confidence: 49%

Section: Potential Energy Surfacesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Quantum dynamics study of H + DBr and D + HBr reaction

Zhang

Jia

et al. 2014

J Mol Model

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“…Numerous approaches have been proposed to model diabatic states. 10,22–28,8,29–33,4,19,34–41 A thorough comparison of these methods is beyond the scope of this work, but, instead, we roughly classify them into two categories on the basis of the relationship between diabatic and adiabatic states: (1) adiabatic-to-diabatic (ATD) and (2) diabatic-at-construction (DAC).…”

Section: Introductionmentioning

confidence: 99%

Diabatic-At-Construction Method for Diabatic and Adiabatic Ground and Excited States Based on Multistate Density Functional Theory

Grofe

Truhlar

et al. 2017

J. Chem. Theory Comput.

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We describe a diabatic-at-construction (DAC) strategy for defining diabatic states to determine the adiabatic ground and excited electronic states and their potential energy surfaces using the multistate density functional theory (MSDFT). The DAC approach differs in two fundamental ways from the adiabatic-to-diabatic (ATD) procedures that transform a set of preselected adiabatic electronic states to a new representation. (1) The DAC states are defined in the first computation step to form an active space, whose configuration interaction produces the adiabatic ground and excited states in the second step of MSDFT. Thus, they do not result from a similarity transformation of the adiabatic states as in the ATD procedure; they are the basis for producing the adiabatic states. The appropriateness and completeness of the DAC active space can be validated by comparison with experimental observables of the ground and excited states. (2) The DAC diabatic states are defined using the valence bond characters of the asymptotic dissociation limits of the adiabatic states of interest, and they are strictly maintained at all molecular geometries. Consequently, DAC diabatic states have specific and well-defined physical and chemical meanings that can be used for understanding the nature of the adiabatic states and their energetic components. Here we present results for the four lowest singlet states of LiH and compare them to a well-tested ATD diabatization method, namely the 3-fold way; the comparison reveals both similarities and differences between the ATD diabatic states and the orthogonalized DAC diabatic states. Furthermore, MSDFT can provide a quantitative description of the ground and excited states for LiH with multiple strongly and weakly avoided curve crossings spanning over 10 Å of interatomic separation.

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Influence of collision energy and vibrational excitation on the dynamics for the H+HBr→H2+Br reaction

et al. 2015

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Quasi-classical trajectory (QCT) calculations of H+HBr→H 2 +Br reaction have been performed on a recently proposed ab initio potential energy surface. The reaction probability and integral cross section are found to be in fairly good agreement with the available quantum mechanical (QM) results on this surface. The behavior of reactivity is well consistent with properties of exothermic reaction. Once the energy of vibrational excited HBr is larger than the barrier height, the integral cross sections for the reaction diverge at very low collision energies close to the threshold, similarly to capture reaction. In addition, differential cross sections show that scattering of the product H 2 shift from backward to forward directions as the collision energy and vibrational quantum number increase. All the theoretical findings are reasonably explained by the properties of the surface, as well as reactive mechanisms.

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Quantum dynamical study of the electronic nonadiabaticity in the D + DBr → Br(Br*) + D2 reaction on new diabatic potential energy surfaces

Cited by 13 publications

References 32 publications

Quantum dynamics study of H + DBr and D + HBr reaction

Quantum dynamics study of H + DBr and D + HBr reaction

Diabatic-At-Construction Method for Diabatic and Adiabatic Ground and Excited States Based on Multistate Density Functional Theory

Influence of collision energy and vibrational excitation on the dynamics for the H+HBr→H2+Br reaction

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