PMID- 17845015
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20071127
LR  - 20070927
IS  - 1089-5639 (Print)
IS  - 1089-5639 (Linking)
VI  - 111
IP  - 39
DP  - 2007 Oct 4
TI  - Microcanonical transition state theory for activated gas-surface reaction 
      dynamics: application to H2/CU(111) with rotation as a spectator.
PG  - 9871-83
AB  - 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.
FAU - Abbott, Heather L
AU  - Abbott HL
AD  - Department of Chemistry, University of Virginia, Charlottesville, Virginia 
      22904-4319, USA.
FAU - Harrison, Ian
AU  - Harrison I
LA  - eng
PT  - Journal Article
DEP - 20070911
PL  - United States
TA  - J Phys Chem A
JT  - The journal of physical chemistry. A
JID - 9890903
EDAT- 2007/09/12 09:00
MHDA- 2007/09/12 09:01
CRDT- 2007/09/12 09:00
PHST- 2007/09/12 09:00 [pubmed]
PHST- 2007/09/12 09:01 [medline]
PHST- 2007/09/12 09:00 [entrez]
AID - 10.1021/jp074038a [doi]
PST - ppublish
SO  - J Phys Chem A. 2007 Oct 4;111(39):9871-83. doi: 10.1021/jp074038a. Epub 2007 Sep 
      11.