An <i>ab initio</i> global potential-energy surface for NH2(A2A′) and vibrational spectrum of the Renner–Teller A2A′-X2A″ system

Zhou, Shulan; Li, Zheng; Xie, Daiqian; Lin, Shi Ying; Guo, Hua

doi:10.1063/1.3125511

Cited by 31 publications

(33 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This barrier is, of course, absent in the usual BO approximation that implies L ab = 0. Zhou et al 29 report a similar effect in the spectroscopy of NH 2 , finding that these diagonal RT terms increase the energy levels of vibrational states with significant amplitude near linearity.…”

Section: B Reaction Probabilities and Wp Time Evolutionsmentioning

confidence: 73%

Nonadiabatic quantum dynamics of C(1D)+H2→CH+H: Coupled-channel calculations including Renner-Teller and Coriolis terms

Defazio

Bussery‐Honvault

Honvault

et al. 2011

The Journal of Chemical Physics

View full text Add to dashboard Cite

The Renner-Teller (RT) coupled-channel dynamics for the C((1)D)+H(2)(X(1)Σ(g) (+))→CH(X(2)Π)+H((2)S) reaction has been investigated for the first time, considering the first two singlet states ã̃(1)A' and b(1)A'' of CH(2) dissociating into the products and RT couplings, evaluated through the ab initio matrix elements of the electronic angular momentum. We have obtained initial-state-resolved probabilities, cross sections and thermal rate constants via the real wavepacket method for both coupled electronic states. In contrast to the N((2)D)+H(2)(X(1)Σ(g)(+)) system, RT effects tend to reduce probabilities, cross sections, and rate constants in the low energy range compared to Born-Oppenheimer (BO) ones, due to the presence of a repulsive RT barrier in the effective potentials and to long-lived resonances. Furthermore, contrary to BO results, the rate constants have a positive temperature dependence in the 100-400 K range. The two-state RT rate constant at 300 K, lower than the BO one, remains inside the error bars of the experimental value.

show abstract

Section: B Reaction Probabilities and Wp Time Evolutionsmentioning

confidence: 73%

Nonadiabatic quantum dynamics of C(1D)+H2→CH+H: Coupled-channel calculations including Renner-Teller and Coriolis terms

Defazio

Bussery‐Honvault

Honvault

et al. 2011

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Now we turn to the H + HN reaction. The PES describing the H + HN reaction 227 is quite different from that for the H + H 2 reaction. It has an intermediate deep potential well of 4.2 eV from H + HN asymptote, and the total reaction probabilities exhibit many resonance peaks.…”

Section: Application Of Typical High-order Split Operators With H + H...mentioning

confidence: 89%

Higher-order split operator schemes for solving the Schrödinger equation in the time-dependent wave packet method: applications to triatomic reactive scattering calculations

Sun

Yang

Zhang

2012

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The efficiency of the numerical propagators for solving the time-dependent Schrödinger equation in the wave packet approach to reactive scattering is of vital importance. In this Perspective, we first briefly review the propagators used in quantum reactive scattering calculations and their applications to triatomic reactions. Then we present a detailed comparison of about thirty higher-order split operator propagators for solving the Schrödinger equation with their applications to the wave packet evolution within a one-dimensional Morse potential, and the total reaction probability calculations for the H + HD, H + NH, H + O(2), and F + HD reactions. These four triatomic reactions have quite different dynamic characteristics and thus provide a comprehensive picture of the relative advantages of these higher-order propagation methods for describing reactive scattering dynamics. Our calculations reveal that the most often used second-order split operator method is typically more efficient for a direct reaction, particularly for those involving flat potential energy surfaces. However, the optimal higher-order split operator methods are more suitable for a reaction with resonances and intermediate complexes or a reaction experiencing potential energy surface with fluctuations of considerable amplitude. Three 4th-order and one 6th-order split operator methods, which are most efficient for solving reactive scattering in various conditions among the tested ones, are recommended for general applications. In addition, a brief discussion on the relative performance between the Chebyshev real wave packet method and the split operator method is given. The results in this Perspective are expected to stimulate more applications of (high-order) split operators to the quantum reactive scattering calculation and other related problems.

show abstract

“…In turn, calculations of PESs for the above two electronic states of

{NH}_{2}

have also been performed by Qu et al using the multireference configuration interaction (MRCI) approach, mostly with the aug‐cc‐pV Q Z (such basis are generally denoted as AV X Z, with X being usually referred to as the basis set cardinal number) and cubic‐spline fits for the representation. Moreover, Zhou et al reported a global PES for based on high‐level ab initio points, which were performed at the MRCI(Q) level (MRCI with the Davidson correction) using an AV Q Z basis set.…”

Section: Introductionmentioning

confidence: 99%

Accurate double many‐body expansion potential energy surface by extrapolation to the complete basis set limit and dynamics calculations for ground state of NH₂

Yuan

Chen

et al. 2013

J Comput Chem

View full text Add to dashboard Cite

An accurate single-sheeted double many-body expansion potential energy surface is reported for the title system. A switching function formalism has been used to warrant the correct behavior at the H2(X1Σg+)+N(2D) and NH (X3Σ-)+H(2S) dissociation channels involving nitrogen in the ground N(4S) and first excited N(2D) states. The topographical features of the novel global potential energy surface are examined in detail, and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. The novel surface can be using to treat well the Renner-Teller degeneracy of the 12A″ and 12A' states of NH 2. Such a work can both be recommended for dynamics studies of the N(2D)+H2 reaction and as building blocks for constructing the double many-body expansion potential energy surface of larger nitrogen/hydrogen-containing systems. In turn, a test theoretical study of the reaction N(2D)+H2(X1Σg+)(ν=0,j=0)→NH (X3Σ-)+H(2S) has been carried out with the method of quantum wave packet on the new potential energy surface. Reaction probabilities, integral cross sections, and differential cross sections have been calculated. Threshold exists because of the energy barrier (68.5 meV) along the minimum energy path. On the curve of reaction probability for total angular momentum J = 0, there are two sharp peaks just above threshold. The value of integral cross section increases quickly from zero to maximum with the increase of collision energy, and then stays stable with small oscillations. The differential cross section result shows that the reaction is a typical forward and backward scatter in agreement with experimental measurement result.

show abstract

An ab initio global potential-energy surface for NH2(A2A′) and vibrational spectrum of the Renner–Teller A2A′-X2A″ system

Cited by 31 publications

References 55 publications

Nonadiabatic quantum dynamics of C(1D)+H2→CH+H: Coupled-channel calculations including Renner-Teller and Coriolis terms

Nonadiabatic quantum dynamics of C(1D)+H2→CH+H: Coupled-channel calculations including Renner-Teller and Coriolis terms

Higher-order split operator schemes for solving the Schrödinger equation in the time-dependent wave packet method: applications to triatomic reactive scattering calculations

Accurate double many‐body expansion potential energy surface by extrapolation to the complete basis set limit and dynamics calculations for ground state of NH₂

Contact Info

Product

Resources

About

An ab initio global potential-energy surface for NH2(A2A′) and vibrational spectrum of the Renner–Teller A2A′-X2A″ system

Cited by 31 publications

References 55 publications

Nonadiabatic quantum dynamics of C(1D)+H2→CH+H: Coupled-channel calculations including Renner-Teller and Coriolis terms

Nonadiabatic quantum dynamics of C(1D)+H2→CH+H: Coupled-channel calculations including Renner-Teller and Coriolis terms

Higher-order split operator schemes for solving the Schrödinger equation in the time-dependent wave packet method: applications to triatomic reactive scattering calculations

Accurate double many‐body expansion potential energy surface by extrapolation to the complete basis set limit and dynamics calculations for ground state of NH2

Contact Info

Product

Resources

About

Accurate double many‐body expansion potential energy surface by extrapolation to the complete basis set limit and dynamics calculations for ground state of NH₂