TY - JOUR
T1 - Optically Activated Functionalization Reactions in Si Quantum Dots
AU - Reboredo, Fernando A.
AU - Schwegler, Eric
AU - Galli, Giulia
PY - 2003/12/10
Y1 - 2003/12/10
N2 - Using ab initio calculations, we have studied the influence of optical activation on functionalization reactions of silicon quantum dots with unsaturated hydrocarbons. We find that the energy barrier for the replacement of silicon-hydrogen with silicon-carbon bonds is dramatically reduced if the silicon dot is optically excited. These results provide an explanation for recent experiments on optically excited porous silicon. In addition, our calculations point at the existence of an intermediate spin-polarized state formed by the dot and an alkene or alkyne, upon relaxation after absorbing a photon. This state could be detected experimentally, by, for example, electron spin resonance measurements. Based on the results of our calculations as a function of the dot size, varied from 0.8 to 1.5 nm, we propose that light activated reactions could be used to functionalize and size select silicon quantum dots at the same time.
AB - Using ab initio calculations, we have studied the influence of optical activation on functionalization reactions of silicon quantum dots with unsaturated hydrocarbons. We find that the energy barrier for the replacement of silicon-hydrogen with silicon-carbon bonds is dramatically reduced if the silicon dot is optically excited. These results provide an explanation for recent experiments on optically excited porous silicon. In addition, our calculations point at the existence of an intermediate spin-polarized state formed by the dot and an alkene or alkyne, upon relaxation after absorbing a photon. This state could be detected experimentally, by, for example, electron spin resonance measurements. Based on the results of our calculations as a function of the dot size, varied from 0.8 to 1.5 nm, we propose that light activated reactions could be used to functionalize and size select silicon quantum dots at the same time.
UR - http://www.scopus.com/inward/record.url?scp=0344667426&partnerID=8YFLogxK
U2 - 10.1021/ja035254+
DO - 10.1021/ja035254+
M3 - Article
AN - SCOPUS:0344667426
SN - 0002-7863
VL - 125
SP - 15243
EP - 15249
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -