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Semirigid vibrating rotor target calculation for reaction O(3P)+CH4CH3+OH

LIU Xinguo, BAI Lihua & ZHANG Qinggang
Department of Physics, Shandong Normal University, Jinan 250014, China Correspondence should be addressed to Liu Xinguo (email: liuxinguo@sdnu.edu.cn) Received November 3, 2003

CH3+OH is made, using of the semirigid vibrating rotor target (SVRT) model and the time-dependent wave packet (TDWP) method. The corresponding reaction probabilities of different initial states are provided. From the calculation of initial rovibrational state j = 0, v = 0, 1, we can see that the excitation of the H-CH3 stretching vibration gives significant enhancement of reaction probability and the reaction threshold decreases dramatically with the enhancement of the vibrating excitation, which indicates that the vibrating energy of reagent molecules contributes a lot to the molecular collision. As for the calculation of reaction probability of state v = 0, j = 0,1,2,3, the results show that the reaction probability rises significantly with the enhancement of rotational quantum number j while the reaction threshold has no changes. The spatial steric effect of the title reaction is studied and analyzed too after the calculation of reaction probability of states j = 5, k = 02, n = 0 and j = 5, k = 2, n = 02 is made.
Keywords: SVRT model, time-dependent wave packet, reaction probability, steric effect. DOI: 10.1360/ 03yw0142

Abstract The time-dependent quantum dynamics calculation for reaction O(3P)+CH4

Introduction

The calculation of polyatomic molecule plays an important role in the molecular reaction dynamics. Since most reactions concerned by chemistry and biology are beyond tetra-atomic, it is quite necessary, for the purpose of accurate quantum calculation, to develop a practical computational methodology, which is adaptive to polyatomic mole cules. In recent years, a number of reduced dimensionality approaches[1 5] have been proposed to treat polyatomic systems, tetra-atomic systems in particular, and some good results have been obtained[3,6]. Currently, the semirigid vibrating rotor target (SVRT) model[7] has been proposed to treat reactive scattering of polyatomic molecules. The SVRT model, which is a reduced dimensionality model that is general for studying collision reaction dynamics of polyatomic systems, has been successfully applied to some reactions[8,9]. Reaction O(3P)+CH4 CH3+OH is a typical abstraction reaction of Hydrogen, which is a primary step in methane combustion. Theoretical dynamics studies
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have also been reported for this reaction[10,11]. In this paper, the SVRT model is applied to studying the reaction of O(3P)+CH4 CH3+OH using TDWP method[12]. The corresponding quantum dynamics results of initial state-selected are calculated. We investigate the influence of vibrational and rotational excitation on the reaction probabilities as well as of the spatial steric effect for the title reaction. 2 2.1 SVRT model applying to reaction of O(3P)+CH4 CH3+OH SVRT model and the Hamiltonian for the atom-polyatom reaction

In the SVRT model, the target molecule, whose spatial motion, including the one-dimensional relative motion (vibration) and the rotation along the molecular axis, can be considered as a motion of a dissymmetric rotor, is therefore treated as a semirigid vibrating rotor. In the basic SVRT model for atom-polyatom reactions, the Hamiltonian for reactive collision between the atomic projectile A(O) and the SVRT molecule T(CH4) takes the form H ap = where = 2 L2 + + HT + V , 2 R 2 2 R 2
2

(1)

M O M CH 4 M O + M CH 4

is the reduced mass of reaction systems, R is the relative radial

distance between the CMS (center-of-mass) of CH4 and O, L is the orbital angular momentum operator. The internal Hamiltonian H describing the target molecule CH4
T

is given by
2 1 2 + VT (r ), H T = i Gij j 2 ij 2 T r 2

(2)

The first term in eq. (2) is the rotational energy of target molecule, the second term in eq. (2) is the relative translational energy between CH3 and H, the third term in eq. (2) is the one-dimensional interaction potential between CH3 fragments and H, where r is the radial distance between the CMS of CH3 M H M CH3 and H, T = is the reduced M H + M CH 3 mass between fragments CH3 and H. The Jacobi coordinates for the O(3P)+CH4 system are shown in fig. 1. As shown in fig. 1, the interaction potential V depends on four

Fig. 1. SVRT model applying to reaction of O(3P) + CH4.

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internal coordinates (R, r, , ), where the polar angle specifies the angle between the vectors R and r, and the angle specifies the rotation of molecule CH4 along its molecule axis r. 2.2 TD wave packet propagation In the TD approach, one solves the TD Schrdinger equation

(t ) = H (t ) t

(3)

with the Hamiltonian defined in eq. (1). The expansion of TD wave function (t) can take the form

(t ) =

U vp ( R)Z JM( n) ( , , )v (r )C pvjkn (t ), jk

pvlkn

(4)

where U v ( R ) is the translational basis function whose definition is given in ref. [12], p

v (r) is vibrational basis function and Z JMn ) ( , , ) is the body-fixed (BF) total jk (
angular momentum eigenfunction. The total angular momentum eigenfunction takes the form,
J* j Z JMn ) ( , , ) = DMK ( )d kn* ( ) jk (

1 2

ein .

(5)

The TD wave-packet is propagated by employing the split-operator method,

(t + ) = eiH 0 / 2 eiu eiH 0 / 2 (t ),

(6)

where the operator H 0 can be defined as

H0 =
2

2M

2 R

2 + VT (r ). 2T r 2

(7)

The generalized potential operator U is defined as U = H rot + V = 1 L2 + i Gij j + V . 2 2 ij 2 R (8)

jk The exact rovibrational eigenfunction, denoted by vn (T , r ), of the SVRT

molecule T satisfies the Schrdinger equation

2 1 jk 2 jk + VT (r ) vn (T , r ) = Evjn vn (T , r ). i Gij j 2 2 ij 2 T r

(9)

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Here j and K are, respectively, quantum numbers of the angular momentum of CH4 and its projection on the body-fixed (BF) R-axis, n is the projection on the H-CH3 molecular axis.
3 Results and discussions

The SVRT model described above, in which only four dimensions of freedom of the 12 internal coordinates are chosen, is applied to the quantum dynamics calculation, based on the Jordan and Gilbert Ab initio PES[3], for reaction O(3P)+CH4 CH3+OH. In order to preserve the C3v symmetry of the target molecule H-CH3 throughout the reaction process, both the angle between every two C-H bonds of the CH3 fragments and the bond-length should be equal to the transitional state of 107.45 and 2.067 Bohr so that the barrier of 10.7 kcal/mol, which is the closest to the experimental value of 8.711.7 kcal/mol, can be obtained. A total of 30 vibrational basis functions are used in the expansion for the r-dependence of the wave function. The maximum rotational quantum state of the CH4 molecule included in the basis expansion is j = 35, which is sufficient to give converged result. A total of 120 sine basis functions spanning in translational coordinate R are used in the wave function expansion. The initial wave packet is located at R = 8.0 Bohr. Since each hydrogen atom in CH4 contributes similarly to the reaction probability, dynamics results should be multiplied by 4. 3.1 Reaction probability of ground state As shown in fig. 2, after calculating the reaction probability of the target molecule

Fig. 2. Reaction probability as a function of translation energy from initial rovibrational state j=0, v=0 and 1.

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in the ground state, we can see that there already exists some non-zero reaction probability when the translational energy is 0.464 eV below the barrier and the reaction probability has arrived at 0.048 when the translational energy approaches the barrier, which indicates that the quantum tunneling effect is quite pronounced. Moreover, the reaction probability shows a peak near the collision energy of 0.43 eV. The reaction probability enhances as translational energy increases. 3.2 Effect of vibrational excitation We calculated reaction probabilities for reaction O(3P)+CH4 from the first excited state of reactive molecule CH4. Here the vibrational quantum v denotes the pseudo vibrational mode between the reacting hydrogen atom and the CH3 group. The reaction probabilities are calculated for initial vibrational states v = 0,1 with its rotational state fixed at j = 0 as a function of collision energy and the results are shown in fig. 2. From fig. 2, we observed the following: Reaction probability is significantly enhanced as vibrational quantum number increases and the reaction threshold is significantly reduced. The reaction threshold of ground state is 0.35 eV while the reaction threshold of the first vibrational excited state is 0.22 eV. That is to say, the reaction threshold is reduced by 0.13 eV when v increases from 0 to 1. The vibrational excitation of reactive molecule contributes significantly to the breaking of C-H bonding. In addition, the reaction probability shows a peak near the collision energy of 0.24 eV comparing the results of the first excited state with those of ground state. 3.3 Effect of rotational excitation We calculated reaction probabilities for reaction O(3P)+CH4 with various initial rotational excitations. Fig. 3 shows the calculated reaction probabilities from initial rotational states j = 03 at v = 0. From fig. 3 we can see that the reaction probability is increased by more than a factor of 2 when rotational quantum number j increases from 0 to 1. However, the reaction probability makes nearly no changes when j increases from 1 to 2. There is no further increase of reaction probability at relatively low collision energy when j increases from 2 to 3 while the reaction probability actually drops at high collision energies. The reason for this is that the effect of orientation movement of the reagent molecules makes the reaction probability change. For various rotational states, though the reaction probability changes with the translational energy, the reaction threshold has almost no changes. The increase of the rotational energy for reagent molecules has important contribution to the abstraction reaction while it has no effect to the reaction threshold. Moreover, all the reaction probabilities show a peak near the collision energy of 0.43 eV, which is very close to the reaction barrier of the PES. The height of peak increases as j rises from 0 to 2 and drops when j rises from 2 to 3. There is no change to the peak position either. 3.4 Influence of steric effect Next, we examine the initial rotational states K = 0, 1, 2 and j = 5, n = 0 for the
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Fig. 3. Reaction probabilities from initial rotational states j = 03 and K = n = 0.

Fig. 4. Reaction probabilities from initial rotational states K = 02 and j = 5, n = 0.

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O(3P)+CH4 reaction system. We see in fig. 4 that reaction probability drastically increases with the increase of translational energy and decreases with the increment of quantum number K. Since n = 0, that is to say, the projection of angular momentum j on the molecular axis r is zero, the vector j must be perpendicular to the axis r. For K = 0, the vector j is also perpendicular to the vector R. As K increases, the vector j tilts towards R and the relative rotation of R and r vectors is not constrained to a single plane. Obviously, reaction probability can be explained by orientation effect. Fig. 5 shows the calculated reaction probabilities from initial rotational states j = 5, K = 2 and n = 02. From fig. 5 we can see that reaction probability increases with the increase of translational energy as the projection quantum number n increases. But for the case of n = 1, it has the largest probability near threshold energy and the probability also shows a peak near the collision energy. Moreover, the probability for case of K = n = 2 drastically increases as the translational energy increases. The reaction probability even arrives near 1.0 at translational energy 1.23 eV. All of these show that O(3P)+CH4 system has strong space steric effect.

Fig. 5. Reaction probabilities from initial rotational states j = 5 and K = 2, n = 02.

In order to prove the present results to be true and to compare them with other theoretical or experimental results, we also calculated the reaction rate constant of reagent molecule CH4 at the initial ground state. The other theoretical and experimental
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results are in good agreement with our rate constant which is also consistent with that of ref. [9]. We will not provide the detailed results for the purpose of saving the length of this paper.
Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant Nos. 19874040 and 10174046).

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