Microcanonical unimolecular rate theory at surfaces. III. Thermal dissociative chemisorption of methane on Pt(111) and detailed balance

A local hot spot model of gas-surface reactivity is used to investigate the state-resolved dynamics of methane dissociative chemisorption on Pt(111) under thermal equilibrium conditions. Three Pt surface oscillators, and the molecular vibrations, rotations, and the translational energy directed along the surface normal are treated as active degrees of freedom in the 16-dimensional microcanonical kinetics. Several energy transfer models for coupling a local hot spot to the surrounding substrate are developed and evaluated within the context of a master equation kinetics approach. Bounds on the thermal dissociative sticking coefficient based on limiting energy transfer models are derived. The three-parameter physisorbed complex microcanonical unimolecular rate theory (PC-MURT) is shown to closely approximate the thermal sticking under any realistic energy transfer model. Assuming an apparent threshold energy for CH(4) dissociative chemisorption of E(0)=0.61 eV on clean Pt(111), the PC-MURT is used to predict angle-resolved yield, translational, vibrational, and rotational distributions for the reactive methane flux at thermal equilibrium at 500 K. By detailed balance, these same distributions should be observed for the methane product from methyl radical hydrogenation at 500 K in the zero coverage limit if the methyl radicals are not subject to side reactions. Given that methyl radical hydrogenation can only be experimentally observed when the CH(3) radicals are kinetically stabilized against decomposition by coadsorbed H, the PC-MURT was used to evaluate E(0) in the high coverage limit. A high coverage value of E(0)=2.3 eV adequately reproduced the experimentally observed methane angular and translational energy distributions from thermal hydrogenation of methyl radicals. Although rigorous application of detailed balance arguments to this reactive system cannot be made because thermal decomposition of the methyl radicals competes with hydrogenation, approximate applicability of detailed balance would argue for a strong coverage dependence of E(0) with H coverage--a dependence not seen for methyl radical hydrogenation on Ru(0001), but not yet experimentally explored on Pt(111).     

Microcanonical transition state theory for activated gas-surface reaction dynamics: application to H2/CU(111) with rotation as a spectator

A microcanonical unimolecular rate theory (MURT) model incorporating quantized surface vibrations and Rice-Ramsperger-Kassel-Marcus rate constants is applied to a benchmark system for gas-surface reaction dynamics, the activated dissociative chemisorption and associative desorption of hydrogen on Cu(111). Both molecular translation parallel to the surface and rotation are treated as spectator degrees of freedom. MURT analysis of diverse experiments indicates that one surface oscillator participates in the dissociative transition state and that the threshold energy for H2 dissociation on Cu(111) is E0 = 62 kJ/mol. The spectator approximation for rotation holds well at thermally accessible rotational energies (i.e., for Er less than approximately 40 kJ/mol). Over the temperature range from 300 to 1000 K, the calculated thermal dissociative sticking coefficient is ST = S0 exp(-Ea/kBT) where S0 = 1.57 and Ea = 62.9 kJ/mol. The sigmoid shape of rovibrational eigenstate-resolved dissociative sticking coefficients as a function of normal translational energy is shown to derive from an averaging of the microcanonical sticking coefficient, with threshold energy E0, over the thermal surface oscillator distribution of the gas-surface collision complexes. Given that H2/Cu(111) is one of the most dynamically biased of gas-surface reactive systems, the simple statistical MURT model simulates and broadly rationalizes the H2/Cu(111) reactive behavior with remarkable fidelity.     

Dynamically biased RRKM model of activated gas-surface reactivity: vibrational efficacy and rotation as a spectator in the dissociative chemisorption of CH4 on Pt(111)

The reactivity of CH(4) impinging on a Pt(111) surface was examined using a precursor-mediated microcanonical trapping model of dissociative chemisorption wherein the effects of rotational and vibrational energy could be explored. Dissociative sticking coefficients for a diverse range of non-equilibrium effusive beam, supersonic beam, and eigenstate-resolved experiments were simulated and an average relative discrepancy between theory and experiment of better than 50% was achieved by treating molecular rotations and translation parallel to the surface as spectator degrees of freedom, and introducing a dynamically-biased vibrational efficacy. The model parameters are {E(0) = 57.9 kJ mol(-1), s = 2, η(v) = 0.40} where E(0) is the apparent threshold energy for reaction, s is the number of surface oscillators participating in energy exchange within each gas-surface collision complex formed, and η(v) is the mean vibrational efficacy for reaction relative to normal translational energy which figures in the assembly of the active exchangeable energy which is available to surmount the activation barrier to dissociative chemisorption. GGA-DFT electronic structure calculations provided vibrational frequencies for the transition state for dissociative chemisorption. The asymmetry of the rotational state populations in supersonic and effusive molecular beam experiments allowed kinetic analysis to establish that taking rotation as a spectator degree of freedom is a good approximation. Surface phonons, rather than the incident molecules, are calculated to play the dominant role in supplying the energy required to overcome the activation barrier for dissociative chemisorption under the thermal equilibrium conditions relevant to high pressure catalysis. Over the temperature range 300 K ≤T≤ 1000 K, the thermal dissociative sticking coefficient is predicted to be well described by S(T) = S(0) exp(-E(a)/RT) where S(0) = 0.62 and E(a) = 62.6 kJ mol(-1).     

Dissociative chemisorption and energy transfer for methane on Ir(111)

A 3-parameter local hot spot model of gas-surface reactivity is employed to analyze and predict dissociative sticking coefficients for CH(4) incident on Ir(111) under varied nonequilibrium and equilibrium conditions. One Ir surface oscillator and the molecular vibrations, rotations, and translational energy directed along the surface normal are treated as active degrees of freedom in the 14 dimensional microcanonical kinetics. The threshold energy for CH(4) dissociative chemisorption on Ir(111) derived from modeling molecular beam experiments is E(0) = 39 kJ/mol. Over more than 4 orders of magnitude of variation in sticking, the average relative discrepancy between the beam and theoretically derived sticking coefficients is 88%. The experimentally observed enhancement in dissociative sticking as beam translational energies decrease below approximately 10 kJ/mol is consistent with a parallel dynamical trapping/energy transfer channel that likely fails to completely thermalize the molecules to the surface temperature. This trapping-mediated sticking, indicative of specific energy transfer pathways from the surface under nonequilibrium conditions, should be a minor contributor to the overall dissociative sticking at thermal equilibrium. Surprisingly, the CH(4) dissociative sticking coefficient predicted for Ir(111) surfaces at thermal equilibrium, based on the molecular beam experiments, is roughly 4 orders of magnitude higher than recent measurements on supported nanoscale Ir catalysts at 1 bar pressure, which suggests that substantial improvements in catalyst turnover rates may be possible.     

Nonequilibrium activated dissociative chemisorption: SiH4 on Si(100)

A three-parameter local hot spot model of gas-surface reactivity is employed to analyze and predict dissociative sticking coefficients for SiH4 incident on Si(100) under varied nonequilibrium conditions. Two Si surface oscillators and the molecular vibrations, rotations, and translational energy directed along the local surface normal are active degrees of freedom in the 15 dimensional microcanonical kinetics. The threshold energy for SiH4 dissociative chemisorption is found to be 19 kJ/mol, in quantitative agreement with recent GGA-DFT calculations. A simple scheme for increasing the rate of chemical vapor deposition of silicon from SiH4 at low surface temperatures is modeled.     

Effusive molecular beam study of C2H6 dissociation on Pt(111)

The dissociative sticking coefficient for C2H6 on Pt(111) has been measured as a function of both gas temperature (Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated ambient gas dosing methods. A microcanonical unimolecular rate theory (MURT) model of the reactive system is used to extract transition state properties from the data as well as to compare our data directly with supersonic molecular beam and thermal equilibrium sticking measurements. We report for the first time the threshold energy for dissociation, E0 = 26.5 +/- 3 kJ mol(-1). This value is only weakly dependent on the other two parameters of the model. A strong surface temperature dependence in the initial sticking coefficient is observed; however, the relatively weak dependence on gas temperature indicates some combination of the following (i) not all molecular excitations are contributing equally to the enhancement of sticking, (ii) that strong entropic effects in the dissociative transition state are leading to unusually high vibrational frequencies in the transition state, and (iii) energy transfer from gas-phase rovibrational modes to the surface is surprisingly efficient. In other words, it appears that vibrational mode-specific behavior and/or molecular rotations may play stronger roles in the dissociative adsorption of C2H6 than they do for CH4. The MURT with an optimized parameter set provides for a predictive understanding of the kinetics of this C-H bond activation reaction, that is, it allows us to predict the dissociative sticking coefficient of C2H6 on Pt(111) for any combination of Ts and Tg even if the two are not equal to one another.     

The dissociative chemisorption of methane on Ni(100): reaction path description of mode-selective chemistry

We derive a model for the dissociative chemisorption of methane on a Ni(100) surface, based on the reaction path Hamiltonian, that includes all 15 molecular degrees of freedom within the harmonic approximation. The total wavefunction is expanded in the adiabatic vibrational states of the molecule, and close-coupled equations are derived for wave packets propagating on vibrationally adiabatic potential energy surfaces, with non-adiabatic couplings linking these states to each other. Vibrational excitation of an incident molecule is shown to significantly enhance the reactivity, if the molecule can undergo transitions to states of lower vibrational energy, with the excess energy converted into motion along the reaction path. Sudden models are used to average over surface impact site and lattice vibrations. Computed dissociative sticking probabilities are in good agreement with experiment, with respect to both magnitude and variation with energy. The ν(1) vibration is shown to have the largest efficacy for promoting reaction, due to its strong non-adiabatic coupling to the ground state, and a significant softening of the vibration at the transition state. Most of the reactivity at 475 K is shown to result from thermally assisted over-the-barrier processes, and not tunneling.     

The role of rotational excitation in the activated dissociative chemisorption of vibrationally excited methane on Ni(100)

We have measured the sticking probability of methane excited to v = 1 of the v3 antisymmetric C-H stretching vibration on a clean Ni(100) surface as a function of rotational state (J = 0, 1, 2 and 3) and have investigated the effect of Coriolis-mixing on reactivity. The data span a wide range of kinetic energies (9-49 kJ mol-1) and indicate that rotational excitation does not alter reactivity by more than a factor of two, even at low molecular speeds that allow for considerable rotation of the molecule during the interaction with the surface. In addition, rotation-induced Coriolis-splitting of the v3 mode into F+, F0 and F- states does not significantly affect the reactivity for J = 1 at 49 kJ mol-1 translational energy, even though the nuclear motions of these states differ. The lack of a pronounced rotational energy effect in methane dissociation on Ni(100) suggests that our previous results for (v = 1, v3, J = 2) are representative of all rovibrational sublevels of this vibrational mode. These experiments shed light on the relative importance of rotational hindering and dynamical steering mechanisms in the dissociative chemisorption on Ni(100) and guide future attempts to accurately model methane dissociation on nickel surfaces.     

Dynamics of analyte binding onto a metallophthalocyanine: NO/FePc

The gas-surface reaction dynamics of NO impinging on an iron(II) phthalocyanine (FePc) monolayer were investigated using King and Wells sticking measurements. The initial sticking probability was measured as a function of both incident molecular beam energy (0.09-0.4 eV) and surface temperature (100-300 K). NO adsorption onto FePc saturates at 3% of a monolayer for all incident beam energies and surface temperatures, suggesting that the final chemisorption site is confined to the Fe metal centers. At low surface temperature and low incident beam energy, the initial sticking probability is 40% and decreases linearly with increasing beam energy and surface temperature. The results are consistent with the NO molecule sticking onto the FePc molecules via physisorption to the aromatics followed by diffusion to the Fe metal center, or precursor-mediated chemisorption. The adsorption mechanism of NO onto FePc was confirmed by control studies of NO sticking onto metal-free H2Pc, inert Au111, and reactive Al111.     

Using effusive molecular beams and microcanonical unimolecular rate theory to characterize CH4 dissociation on Pt(111)

The dissociative sticking coefficient for CH4 on Pt(111) has been measured as a function of both gas temperature (Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated ambient gas dosing methods. The experimental results are used to optimize the three parameters of a microcanonical unimolecular rate theory (MURT) model of the reactive system. The MURT calculations allow us to extract transition state properties from the data as well as to compare our data directly to other molecular beam and thermal equilibrium sticking measurements. We find a threshold energy for dissociation of E0 = 52.5 +/- 3.5 kJ mol(-1). Furthermore, the MURT with an optimized parameter set provides for a predictive understanding of the kinetics of this C-H bond activation reaction, that is, it allows us to predict the dissociative sticking coefficient of CH4 on Pt(111) for any combination of Ts and Tg even if the two are not equal to one another, indeed, the distribution of molecular energy need not even be thermal. Comparison of our results to those from recent thermal equilibrium catalysis studies on CH4 reforming over Pt nanoclusters ( approximately 2 nm diam) dispersed on oxide substrates indicates that the reactivity of Pt(111) exceeds that of the Pt nanocatalysts by several orders of magnitude.     

Seven-dimensional microcanonical treatment of hydrogen dissociation dynamics on Cu(111): clarifying the essential role of surface phonons

A simple picture of the hydrogen dissociation/associative desorption dynamics on Cu(111) emerges from a two-parameter, full dimensionality microcanonical unimolecular rate theory (MURT) model of the gas-surface reactivity. Vibrational frequencies for the reactive transition state were taken from density functional theory calculations of a six-dimensional potential energy surface [Hammer et al., Phys. Rev. Lett. 73, 1400 (1994)]. The two remaining parameters required by the MURT were fixed by simulation of experiments. These parameters are the dissociation threshold energy, E(0)=79 kJmol, and the number of surface oscillators involved in the localized H(2)Cu(111) collision complex, s=1. The two-parameter MURT quantitatively predicts much of the varied behavior observed for the H(2) and D(2)Cu(111) reactive systems, including the temperature-dependent associative desorption angular distributions, mean translational energies of the associatively desorbing hydrogen as a function of rovibrational eigenstate, etc. The divergence of the statistical theory's predictions from experimental results at low rotational quantum numbers, J < or approximately 5, suggests that either (i) rotational steering is important to the dissociation dynamics at low J, an effect that washes out at high J, or (ii) molecular rotation is approximately a spectator degree of freedom to the dissociation dynamics for these low J states, the states that dominate the thermal reactivity. Surface vibrations are predicted to provide approximately 30% of the energy required to surmount the activation barrier to H(2) dissociation under thermal equilibrium conditions. The MURT with s=1 is used to analytically confirm the experimental finding that partial differential "E(a)(T(s))" partial differential E(t)= -1 for eigenstate-resolved dissociative sticking at translational energies E(t)相似文献   

平动能对激光诱导气-固表面蚀刻反应的增强效应

本文采用超声分子束和时间分辨质谱技术研究了入射分子平动能对激光诱导气-固表面反应的增强效应. 对于由可见激光(56 nm)诱导的Cl_2与Ge(111)、Si(111)和GaAS(100)表面蚀刻反应, 研究发现提高Cl_2分子的入射平功能将明显地增加反应产率, 而且都存在一个入射平动能的反应阈值, 其数值为5～7 kJ·mol~(-1). 此外, 从反应产物的飞行时间谱测得入射分子平动能对产物平动温度的影响. 这些结果可以通过平动能促进Cl_2分子在表面上解离化学吸附过程来解释。     

甲烷在Ni表面及La薄膜上激活解离化学吸附

利用分子束技术改变甲烷的平动能E_k来研究E_k及其法向分量E_n对甲烷在Ni表面及La薄膜上激活解离吸附的影响。对CH_4/Ni及CH_4/La系统, 当甲烷的平动能E_k分别低于58.5 kJ·mol~(-1)及52.3 kJ·mol~(-1)时, 没观察到甲烷的解离吸附。当甲烷的平动能超过此阈值时, 即对CH_4/Ni系统, 当Ek=58.5增至63.8 kJ·mol~(-1)时, 初始沾着几率s_0由0至0.54线性增加; 对CH_4/La系统, 当E_k=52.3增至63.8 kJ·mol~(-1)时, S_0由0至0.49线性增加。这些结果表明, 两个系统的化学吸附是不经过前趋态的直接化学吸附。最后求出CH_4/Ni, CH_4/La系统的表观活化能分别为46.8 kJ·mol~(-1)和38.1 kJ·mol~(-1)。     

1064nm激光诱导Ge(111)与Cl2反应动力学

采用超声分子束和时间分辨质谱技术研究了1064nm脉冲激光辐照下Ge(111)与Cl₂的反应动力学。实验结果表明,该反应的主要产物为GeCl₂,提高入射氯分子的平动能将增加反应速率。激光能量密度对GeCl₂产率呈指数关系,而对GeCl₂的平动温度影响不大。升高Ge(111)表面温度也能提高反应产率。同时还讨论了近红外激光诱导GeCl₂反应的机理。     

Microcalorimetry of oxygen adsorption on fcc Co{110}

The coverage dependent heats of adsorption and sticking probabilities for oxygen on fcc Co{110} have been measured at 300 K using single crystal adsorption calorimetry (SCAC). Initial adsorption is consistent with dissociative chemisorption at low coverage followed by oxide formation above 0.6 ML coverage. The initial heat of adsorption of 633 kJ mol(-1) is similar to heat values calorimetrically measured on other ferromagnetic metal surfaces, such as nickel and iron. As the coverage increases, the heat of adsorption and sticking probability drop very rapidly up to the onset of oxidation. As already observed for other oxygen-metal surface systems, strong lateral adatom repulsions are responsible for the transition from the chemisorption regime to oxide film formation at higher coverage. The heat of oxide formation at the onset is 475 kJ mol(-1), which is consistent with the formation of CoO crystallites. The oxide film formation is discussed in terms of nucleation and island growth, and the Mott-Cabrera mechanisms, the latter being evidenced by the relatively constant heat of adsorption and sticking probability in contrast to the nickel and iron oxidation cases.     

Communication: angle-resolved thermal dissociative sticking of CH4 on Pt(111): further indication that rotation is a spectator to the gas-surface reaction dynamics

Effusive molecular beam measurements of angle-resolved thermal dissociative sticking coefficients for CH(4) impinging on a Pt(111) surface, at a temperature of 700 K, are reported and compared to theoretical predictions. The reactivity falls off steeply as the molecular angle of incidence increases away from the surface normal. Successful modeling of the thermal dissociative sticking behavior, consistent with existent CH(4) supersonic molecular beam experiments involving rotationally cold molecules, required that rotation be treated as a spectator degree of freedom.     

A mass spectrometric and density functional study of the intermetallic molecules AuBe, AuMg, and AuCa

The intermetallic molecules AuBe and AuCa were identified by means of the Knudsen-Effusion Mass Spectrometry technique in the high-temperature vapors produced by vaporizing Au-Be-Ca alloys of proper composition. The gaseous equilibria AuBe(g)+Au(g)=Au(2)(g)+Be(g) and AuCa(g)+Au(g)=Au(2)(g)+Ca(g) were studied in the temperature ranges 1720-1841 K and 1669-1841 K, respectively, by monitoring the partial pressures of all the species involved. The equilibrium data were analyzed by the third-law method, obtaining for the first time the dissociation energy D(0) ( composite function) of the two intermetallic species: D(0) ( composite function)(AuBe)=234.0+/-4.0 kJ/mol; D(0) ( composite function)(AuCa)=246.7+/-4.0 kJ/mol. These values are significantly higher than the recently published D(0) ( composite function) of the species AuMg (175.4+/-2.7 kJ/mol). Furthermore, the ionization energies (IE) of AuBe, AuMg, and AuCa were obtained by measuring the electron impact ionization efficiency curves, IE(AuBe)=7.5+/-0.3 eV, IE(AuMg)=6.7+/-0.3 eV, and IE(AuCa)=5.5+/-0.3 eV. Theoretical calculations were also carried out for these species by density functional theory methods (PW91 and BP86) used in conjunction with Stuttgart relativistic effective core potentials. Both functionals were found to perform very well in reproducing experimental D(0) ( composite function), IE, and molecular parameters.     

Adsorption dynamics of water on Pt{110}-(1 x 2)

The dynamics of H(2)O adsorption on Pt{110}-(1 x 2) is studied using supersonic molecular beam and temperature programed desorption techniques. The sticking probabilities are measured using the King and Wells method at a surface temperature of 165 K. The absolute initial sticking probability s(0) of H(2)O is 0.54+/-0.03 for an incident kinetic energy of 27 kJmol. However, an unusual molecular beam flux dependence on s(0) is also found. At low water coverage (theta<1), the sticking probability is independent of coverage due either to diffusion in an extrinsic precursor state formed above bilayer islands or to incorporation into the islands. We define theta=1 as the water coverage when the dissociative sticking probability of D(2) on a surface predosed with water has dropped to zero. The slow falling H(2)O sticking probability at theta>1 results from compression of the bilayer and the formation of multilayers. Temperature programed desorption of water shows fractional order kinetics consistent with hydrogen-bonded islands on the surface. A remarkable dependence of the initial sticking probability on the translational (1-27 kJ/mol) and internal energies of water is observed: s(0) is found to be essentially a step function of translational energy, increasing fivefold at a threshold energy of 5 kJ/mol. The threshold migrates to higher energies with increasing nozzle temperature (300-700 K). We conclude that both rotational state and rotational alignment of the water molecules in the seeded supersonic expansion are implicated in dictating the adsorption process.     

Direct sticking and differential adsorption heats as probes of structural transitions: O2 on the stepped Ni[211] surface

Coverage-dependent heats of adsorption and sticking probabilities for oxygen on Ni[211] have been measured at 300 K using single-crystal adsorption calorimetry. The data are consistent with a switch from dissociative chemisorption at low coverage to oxide formation above 2 ML adatom coverage. The initial heat of adsorption is 620 kJ mol(-)(1), considerably higher than for any low Miller index nickel surface; this is attributed to the presence of low coordination step atoms that are preferably occupied up to 1 ML. As the coverage increases, the heat is found to drop very rapidly, indicating the presence of strong lateral adatom repulsions, which ultimately drive a transition from the chemisorption regime to oxide film formation at higher coverage. The shape of the coverage-dependent sticking probability is consistent with a direct adsorption mechanism at low coverage. At higher coverage, the transition between the chemisorption and oxidation regimes is relatively complex compared with low Miller index nickel surfaces. This is discussed in terms of the influence of the step sites on the [211] surface.