Path-integral molecular dynamics simulations of small hydrated sulfuric acid clusters HSO(HO) (=1-6) on semiempirical PM6 potential surfaces

Kakizaki, Akira*; Motegi, Haruki*; Yoshikawa, Takehiro*; Takayanagi, Toshiyuki*; Shiga, Motoyuki   ; Tachikawa, Masanori*

Quantum path-integral molecular dynamics simulations for a series of sulfuric acid clusters, HSO(HO)(=1-6), were performed using semiempirical PM6 method. It was found that the acid dissociation probability increases with an increase in the cluster size, and that so-called contact-ion-pair structures are dominant in the proton-dissociated clusters. The importance of nuclear quantum effects in the cluster structures and proton-transfer processes is demonstrated.