Date: 22 Nov 2011

Importance of shattering fragmentation in the surface-induced dissociation of protonated octaglycine


A QM + MM direct chemical dynamics simulation was performed to study collisions of protonated octaglycine, gly8-H+, with the diamond {111} surface at an initial collision energy E i of 100 eV and incident angle θ i of 0° and 45°. The semiempirical model AM1 was used for the gly8-H+ intramolecular potential, so that its fragmentation could be studied. Shattering dominates gly8-H+ fragmentation at θ i = 0°, with 78% of the ions dissociating in this way. At θ i = 45° shattering is much less important. For θ i = 0° there are 304 different pathways, many related by their backbone cleavage patterns. For the θ i = 0° fragmentations, 59% resulted from both a-x and b-y cleavages, while for θ i = 45° 70% of the fragmentations occurred with only a-x cleavage. For θ i = 0°, the average percentage energy transfers to the internal degrees of freedom of the ion and the surface, and the energy remaining in ion translation are 45%, 26%, and 29%. For 45° these percentages are 26%, 12%, and 62%. The percentage energy-transfer to ΔE int for θ i = 0° is larger than that reported in previous experiments for collisions of des-Arg1-bradykinin with a diamond surface at the same θ i . This difference is discussed in terms of differences between the model diamond surface used in the simulations and the diamond surface prepared for the experiments.

Published online March 4, 2009