Quantum dynamics of the dissociation of H2 on Cu(100):: Dependence of the site-reactivity on initial rovibrational state

被引:34
作者
McCormack, DA
Kroes, GJ
Olsen, RA
Groeneveld, JA
van Stralen, JNP
Baerends, EJ
Mowrey, RC
机构
[1] Leiden Univ, Leiden Inst Chem, Gorlaeus Labs, NL-2300 RA Leiden, Netherlands
[2] Free Univ Amsterdam, NL-1081 HV Amsterdam, Netherlands
[3] USN, Theoret Chem Sect, Res Lab, Washington, DC 20375 USA
关键词
D O I
10.1039/b002507k
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We perform six-dimensional (6D) quantum wavepacket calculations for H-2 dissociatively adsorbing on Cu(100) from a variety of rovibrational initial states. The calculations are performed on a new potential energy surface (PES), the construction of which is also detailed. Reaction probabilities are in good agreement with experimental findings. Using a new flux analysis method, we calculate the reaction probability density as a function of surface site and collision energy, for a variety of initial states. This approach is used to study the effects of rotation and vibration on reaction at specific surface sites. The results are explained in terms of characteristics of the PES and intrinsically dynamic effects. An important observation is that, even at low collision energies, reaction does not necessarily proceed predominantly in the region of the minimum potential barrier, but can occur almost exclusively at a site with a higher barrier. This suggests that experimental control of initial conditions could be used to selectively induce reaction at particular surface sites. Our predictions for site-reactivity could be tested using contemporary experimental methods: The calculations predict that, for reacting molecules, there will be a dependence of the quadrupole alignment of j on the incident vibrational state, v. This is a direct result of PES topography in the vicinity of the preferred reaction sites of v=0 and v=1 molecules. Invoking detailed balance, evidence for this difference in preferred reaction site of v=0 and 1 molecules could be obtained through associative desorption experiments.
引用
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页码:109 / 132
页数:24
相关论文
共 76 条
[1]   ADSORPTION AND DESORPTION-KINETICS IN THE SYSTEMS H-2/CU(111), H-2/CU(110) AND H-2/CU(100) [J].
ANGER, G ;
WINKLER, A ;
RENDULIC, KD .
SURFACE SCIENCE, 1989, 220 (01) :1-17
[2]  
[Anonymous], [No title captured], DOI DOI 10.1016/0021-9991(92)90277-6
[3]  
[Anonymous], 1961, QUANTUM MECH
[4]   GRID METHODS FOR SOLVING THE SCHRODINGER-EQUATION AND TIME-DEPENDENT QUANTUM DYNAMICS OF MOLECULAR PHOTOFRAGMENTATION AND REACTIVE SCATTERING PROCESSES [J].
BALINTKURTI, GG ;
DIXON, RN ;
MARSTON, CC .
INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY, 1992, 11 (02) :317-344
[5]   TIME-DEPENDENT QUANTUM DYNAMICS OF MOLECULAR PHOTOFRAGMENTATION PROCESSES [J].
BALINTKURTI, GG ;
DIXON, RN ;
MARSTON, CC .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1990, 86 (10) :1741-1749
[6]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[7]   ROTATIONAL COOLING AND HEATING IN ACTIVATED ADSORPTION-DESORPTION FOR D2/CU(111) [J].
BRUNNER, T ;
BRENIG, W .
SURFACE SCIENCE, 1994, 317 (03) :303-308
[8]   THE PURELY FAST DISTRIBUTION OF H-2 AND D2 MOLECULES DESORBING FROM CU(100) AND CU(111) SURFACES [J].
COMSA, G ;
DAVID, R .
SURFACE SCIENCE, 1982, 117 (1-3) :77-84
[9]   Six dimensional quantum dynamics study for dissociative adsorption of H-2 on Cu(111) surface [J].
Dai, JQ ;
Light, JC .
JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (05) :1676-1679
[10]   The steric effect in a full dimensional quantum dynamics simulation for the dissociative adsorption of H2 on Cu(111) [J].
Dai, JQ ;
Light, JC .
JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (18) :7816-7820