Is there a barrier for the C2v insertion reaction in O(1D)+H2? A test dynamics study based on two-valued energy-switching potential energy surfaces

Abstract

We have calculated cross-sections and rate constants for the title reaction by using the quasiclassical trajectory method and a recently reported two-valued energy-switching potential energy surface for the water molecule. By varying the amplitude and rate of decay of a local Gaussian term which controls the appearance of a barrier along the C 2v minimum energy pro®le, an attempt has been made to answer the title issue. A comparison of the calculated rate constants with the available experimental data suggests that the barrier, if existing, lies below the energy of the reactants, and separates the small van der Waals well from the deep chemical one at short distances. Ó

Application of renormalized coupled-cluster methods to potential function of water

“…reaction, which takes place on the ground-state potential energy surface of water, is known to play a significant role in combustion and atmospheric chemistry [113,114]. Two of the dissociation pathways examined in this work, namely, the dissociation of a single O-H bond and the C 2v dissociation path of the water molecule into H 2 (X 1 Σ + g ) and O(2 p 4 1 D) are directly related to this important reaction.…”

“…In the case of another C 2v -symmetric cut, namely cut (iii), we followed the approximate energy path toward the dissociation of the water molecule into H 2 (X 1 Σ + g ) and O(2 p 4 1 D), determined using the potential function of Ref. [102] and defined by the coordinate Y , which is the distance between the O nucleus and the line connecting the H nuclei, and the properly optimized H-O-H angle α [113,114]. The equilibrium values of Y and α are Y e = 0.58641 Å and α e = 104.501 degree.…”

Dynamical studies and product analysis of O(1D) + H2/D2reactions

“…OH þ H and its isotopic variants have been the subject of various experimental studies [1][2][3][4][5][6][7][8]. Numerous theoretical studies of its dynamics have also been carried out (for example, see [1,[5][6][7][9][10][11][12][13][14][15][16][17][18][19][20]) using the potential energy surfaces (PES) published for this system [9,[21][22][23][24][25][26][27][28][29][30][31][32].…”

An Important Well Studied Atmospheric Reaction, <mml:math altimg="si1.gif" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http

“…Varandas [28]; (---) SL1 PES [32]; (-· -·) SL3 PES [32]; (-) ES [21]; (-· · · -· · ·) ES-2v II [25]; (· · ·) ES-2v III [25] and (---) K PES [52]. et al [25] have shown that the reactivity on the ES-2v PES strongly depends on the shape of the small bump for the C 2v insertion. Adding a Gaussian term, they have been able to propose two modifications of this PES, namely ES-2v II and ES-2v III, with different reactivities as shown in this figure.…”

“…Numerous theoretical studies of its dynamics have also been carried out, for example see [11,13,[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31], using several potential energy surfaces (PESs) published for this system [29,[32][33][34][35][36][37][38][39][40][41][42][43]. These works have been the subject of partial reviews by Liu [44], Althorpe and Clary [45], Balucani et al [46] and Aoiz et al [47].…”