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

Abstract

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.

Nonadiabatic dynamics of O(1D) + N2$( {X{}^1\Sigma _g^ + } )\rightarrow $(XΣg+1)→O(3P) + N2$ ( {X{}^1\Sigma _g^ + } )$(XΣg+1) on three coupled potential surfaces: Symmetry, Coriolis, spin-orbit, and Renner-Teller effects

“…We employed our theory of NA effects in triatomic collisions, [19][20][21] ab initio GVS (Ref. 14) and GGS (Ref.…”

Quantum mechanical differential and integral cross sections for the C(1D) + H2(ν = 0, j = 0) → CH(ν′, j′) + H reaction

“…20 Later, the ab initio data for the BHL PES were refitted with the reproducing kernel Hilbert space (RKHS) method to remove some spurious features of the original BHL surface, and the refitted surface is a) Electronic mail: bian@iccas.ac.cn denoted as RKHS PES. 21 Quantum mechanical (QM) 18,20,[22][23][24][25][26][27][28][29][30][31] and quasiclassical trajectory (QCT) 9,18,19,21,23,30 methods, as well as statistical models, [32][33][34][35] have been applied to investigate the title reaction using the aforementioned PESs. Although there are other ab initio-based PESs and subsequent dynamical calculations, [36][37][38] the RKHS PES is the most widely used in dynamical studies.…”

“…40 In addition, the first excited singlet electronic state (1 1 A ′′ ), which may have some contribution to the overall reactivity of the C( 1 D) + H 2 reaction, has also been studied by several groups. 28,30,31,[41][42][43][44] Up to now, the accurate QM product state-resolved integral cross section (ICS) and differential cross section (DCS) have been reported only at the collision energy of 0.080 eV. 23 To gain more insight into its reaction dynamics, it is desirable to investigate the energy dependence of the state-to-state scattering attributes of the title reaction with an accurate QM method.…”

Dynamical importance of van der Waals saddle and excited potential surface in C(1D)+D2 complex-forming reaction

“…have developed a global ab initio PES (called Bussery-Honvault-Honvault-Launay (BHL)) for the state; later, the ab initio data are refitted with the reproducing kernel Hilbert space (RKHS) method to remove some spurious features of the BHL PES, and the modified PES is denoted as the RKHS PES27. Although there are other PESs and subsequent dynamical calculations2829, the RKHS PES is the most widely used in dynamical studies273031323334. Most recently, a highly accurate global ab initio PES (or Zhang-Ma-Bian-a (ZMB-a)) has been constructed by our group35, which is unique in the accurate description of the regions of vdW interactions and around conical intersections (CIs), and further dynamical calculations36 performed on this PES for the C( 1 D )+H 2 reaction confirm its accuracy.…”