Accurate <i>ab initio</i> double many-body expansion potential energy surface for ground-state H2S by extrapolation to the complete basis set limit

Song, Yuzhi; Varandas, A. J. C.

doi:10.1063/1.3103268

Cited by 52 publications

(73 citation statements)

References 61 publications

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“…Given the high level of ab initio calculations used in its construction, one can expect a higher degree of accuracy as compared with previous PESs for the ground 1 1 A state of the SH 2 system. The few dynamical studies available on this PES at the time 30 pointed at different dynamical effects to those calculated on the RKHS PES (Ref. 14) and even with those reported for a similar PES by the same authors 30,32 to be addressed further below.…”

Section: Introductionmentioning

confidence: 82%

“…The few dynamical studies available on this PES at the time 30 pointed at different dynamical effects to those calculated on the RKHS PES (Ref. 14) and even with those reported for a similar PES by the same authors 30,32 to be addressed further below. In particular, the values of their QCT thermal rate constants at 300 K for different isotopes and intramolecular and intermolecular kinetic isotope effects were presented in Ref.…”

Section: Introductionmentioning

confidence: 82%

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On the role of dynamical barriers in barrierless reactions at low energies: S(1D) + H2

Lara

Jambrina

Varandas

et al. 2011

The Journal of Chemical Physics

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Reaction probabilities as a function of total angular momentum (opacity functions) and the resulting reaction cross sections for the collision of open shell S((1)D) atoms with para-hydrogen have been calculated in the kinetic energy range 0.09-10 meV (1-120 K). The quantum mechanical hyperspherical reactive scattering method and quasi-classical trajectory and statistical quasi-classical trajectory approaches were used. Two different ab initio potential energy surfaces (PESs) have been considered. The widely used reproducing kernel Hilbert space (RKHS) PES by Ho et al. [T.-S. Ho, T. Hollebeek, H. Rabitz, S. D. Chao, R. T. Skodje, A. S. Zyubin, and A. M. Mebel, J. Chem. Phys 116, 4124 (2002)] and the recently published accurate double many-body expansion (DMBE)/complete basis set (CBS) PES by Song and Varandas [Y. Z. Song and A. J. C. Varandas, J. Chem. Phys. 130, 134317 (2009)]. The calculations at low collision energies reveal very different dynamical behaviors on the two PESs. The reactivity on the RKHS PES is found to be considerably larger than that on the DMBE/CBS PES as a result of larger reaction probabilities at low total (here also orbital) angular momentum values and to opacity functions which extend to significantly larger total angular momentum values. The observed differences have their origin in two major distinct topographic features. Although both PESs are essentially barrierless for equilibrium H-H distances, when the H-H bond is compressed the DMBE/CBS PES gives rise to a dynamical barrier which limits the reactivity of the system. This barrier is completely absent in the RHKS PES. In addition, the latter PES exhibits a van der Walls well in the entrance channel which reduces the height of the centrifugal barrier and is able to support resonances. As a result, a significant larger cross section is found on this PES, with marked oscillations attributable to shape resonances and/or to the opening of partial wave contributions. The comparison of the results on both PESs is illustrative of the wealth of the dynamics at low collision energy. It is also illuminating about the difficulties encountered in modeling an all-purpose global potential energy surface.

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Section: Introductionmentioning

confidence: 82%

Section: Introductionmentioning

confidence: 82%

On the role of dynamical barriers in barrierless reactions at low energies: S(1D) + H2

Lara

Jambrina

Varandas

et al. 2011

The Journal of Chemical Physics

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“…Had we determined the CRPs on the DMBE/CBS PES, 46 we would have found noteworthy differences with the results obtained on the RKHS and DMBE/SEC PES. This is due to the fit resulting in DMBE/CBS PES that produced some artifacts which amounts to a barrier at compressed H-H internuclear distances.…”

Section: A Cumulative Reaction Probability For J =mentioning

confidence: 58%

“…28,42 It has been also found that, at least at low energies, the reaction takes place mostly via an insertion mechanism involving a long-lived complex. Recent experiments at very low collision energies performed by Costes co-workers 43 and Sims and co-workers 44 as well as the new set of PESs calculated by Song et al, 46,47 as an alternative to the widely used reduced-kernel Hilbert space (RKHS) PES by Ho et al, 30 have attracted a renewed interest on this system. In this paper, we will apply the methodology inherent to the CRP formalism to the S( 1 D) + H 2 reaction.…”

Section: Introductionmentioning

confidence: 99%

Rate coefficients from quantum and quasi-classical cumulative reaction probabilities for the S(1D) + H2 reaction

Jambrina

Lara

Menéndez

et al. 2012

The Journal of Chemical Physics

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Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S( 1 D) + H 2 → SH + H at total energies up to 1.2 eV using three different theoretical approaches: time-independent quantum mechanics (QM), quasiclassical trajectories (QCT), and statistical quasiclassical trajectories ( The results show that the differences between these two PES are relatively minor and mostly related to the different topologies of the well. In addition, the agreement between the three theoretical methodologies is good, even for the highest total angular momenta and energies. In particular, the good accordance between the CRPs obtained with dynamical methods (QM and QCT) and the statistical model (SQCT) indicates that the reaction can be considered statistical in the whole range of energies in contrast with the findings for other prototypical barrierless reactions. In addition, total CRPs and rate coefficients in the range of 20-1000 K have been calculated using the QCT and SQCT methods and have been found somewhat smaller than the experimental total removal rates of S( 1 D).

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“…In order to carry out the extrapolation, electronic energy in the MRCI(Q) calculation is expressed by a sum of two terms [45,51] ,…”

Section: Extrapolation To the Cbs Limitmentioning

confidence: 99%

Accurate potential energy function and spectroscopic properties of NS (X<sup>2</sup>Π) via extrapolation to the complete basis set limit

Guo¹

2017

JAMS

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Abstract. Potential energy curves (PECs) for the ground electronic state of NS are acquired by means of fitting the ab initio energies computed at the multi-reference configuration interaction method with the Davidson correction in combination with a series of correlation-consistent basis sets from Dunning: aug-ccpVXZ (X = T, Q, 5 and 6). In order to obtain PECs with high accuracy, the PECs computed with aug-cc-pV(Q,5)Z basis sets are extrapolated to the complete basis set limit. Such PECs are then used to fit the analytical potential energy functions (APEFs) with the extended Hartree-Fock approximate correlation energy method. Based on the APEFs of NS(X 2 Π), reliable and accurate spectroscopic parameters are obtained. By solving the radial Schrödinger equation numerically, we can acquire the complete set of vibrational levels, inertial rotation constant, centrifugal distortion constants and classical turning points when J = 0. As a whole, our research data can be regarded as a reference for prospective research on the NS molecule.

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Accurate ab initio double many-body expansion potential energy surface for ground-state H2S by extrapolation to the complete basis set limit

Cited by 52 publications

References 61 publications

On the role of dynamical barriers in barrierless reactions at low energies: S(1D) + H2

On the role of dynamical barriers in barrierless reactions at low energies: S(1D) + H2

Rate coefficients from quantum and quasi-classical cumulative reaction probabilities for the S(1D) + H2 reaction

Accurate potential energy function and spectroscopic properties of NS (X<sup>2</sup>Π) via extrapolation to the complete basis set limit

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