Molecular dynamics simulations and potential energy calculations have been performed to investigate the dissociative chemisorption of disilane (Si 2 H 6 ) on the Si(001)2ϫ1 surface. These calculations have been carried out using the extended Brenner ͑XB͒ empirical potential. The minimum energy atomic configurations for SiH 3 , SiH 2 , and H-Si-Si-H ͑Si 2 H 2 ͒ species chemisorbed on the Si(001)2ϫ1 surface have been determined. The chemisorption of SiH 3 radicals has been observed to occur predominantly at the dangling bond sites of the Si͑001͒ surface. The most stable SiH 2 configurations are found to be the on-dimer and intrarow structures. Seven different Si 2 H 2 chemisorption structures have been investigated and the on-dimer-B structure found to be the most energetically favorable. These theoretically predicted structures are discussed in the light of recent experimental studies. Comparison of the results of these XB potential energy calculations with all-electron ab initio cluster calculations has also been made for a number of these different chemisorption structures. ͓S0163-1829͑99͒13135-7͔ PHYSICAL REVIEW B 15 SEPTEMBER 1999-II VOLUME 60, NUMBER 12 PRB 60 0163-1829/99/60͑12͒/8686͑9͒/$15.00 8686