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A Model Calculation for the Isomerization and Decomposition of Chemisorbed HCN on the Si(100)‐2×1 Surface
Author(s) -
BacalzoGladden F.,
Musaev D. G.,
Lin M. C.
Publication year - 1999
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199900055
Subject(s) - chemistry , isomerization , decomposition , adsorption , ab initio , density functional theory , potential energy surface , activation barrier , computational chemistry , cluster (spacecraft) , gas phase , atom (system on chip) , photochemistry , catalysis , organic chemistry , computer science , embedded system , programming language
Ab initio molecular orbital and hybrid density functional theory calculations have been performed to study the adsorption, isomerization, and decomposition of HCN on Si(100)‐2×1 using the Si 9 H 12 cluster model of the surface. The results of our calculations indicate that the HCN can adsorb molecularly without a barrier onto the surface with both end‐on (LM1) and side‐on (LM2) positions. LM1 can isomerize to LM2 with a small barrier of 8 kcal/mol. The isomerization of LM2 by H‐migration from C to the N atom, requires 76 kcal/mol activation energy (c.f. 47.5 kcal/mol in the gas phase) because of surface stabilization. Both HCN(a) and HNC(a) end‐on adsorbates were found to dissociate readily, as concluded in our earlier experiment, to produce H and CN adspecies. The computed vibrational frequencies of HCN, CN, and also HCNH adspecies agree reasonably well with those observed experimentally. HCNH was found to be stable, with either the C or the N attaching to the surface.