title: Electric field-driven acid-base chemistry: proton transfer from acid (HCl) to base (NH3/H2O).
abstract: It is well-known that single H3N-HCl and H2O-HCl acid-base pairs do not react to form the ion pairs, H4N(+)Cl(-) and H3O(+)Cl(-), in isolation. On the basis of ab initio method, we propose a physical method of external electric field (Eext) to drive the proton transfer from acid (HCl) to base (NH3/H2O). Our results show that when Eext along the proton-transfer direction achieves or exceeds the critical electric field (Ec), the proton transfer occurs, such as, the Ec values of proton transfer for H3N-HCl and H2O-HCl are 54 × 10(-4) and 210 × 10(-4) au, respectively. And the degree of the proton transfer can be controlled by modulating the strength of Eext. Furthermore, we estimate the inductive strength of an excess electron (Ee) equivalent to the Eext = 125 × 10(-4) au, which is greater than the Ec (54 × 10(-4) au) of NH3-HCl but less than the Ec (210 × 10(-4) au) of H2O-HCl. This explains well the anion photoelectron spectroscopy [Eustis et al. Science 2008, 319, 936] that an excess electron can trigger the proton transfer for H3N-HCl but not for H2O-HCl. On the basis of the above estimation, we also predict that two excess electrons can induce H2O-HCl to undergo the proton transfer and form the ion pair H3O(+)Cl(-).
authors.affiliation: State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University , Changchun 130023, People's Republic of China.
authors.forename: Zhong-Jun
authors.initials: ZJ
authors.lastname: Zhou
authors.forename: Xiao-Ping
authors.initials: XP
authors.lastname: Li
authors.forename: Zhen-Bo
authors.initials: ZB
authors.lastname: Liu
authors.forename: Zhi-Ru
authors.initials: ZR
authors.lastname: Li
authors.forename: Xu-Ri
authors.initials: XR
authors.lastname: Huang
authors.forename: Chia-Chung
authors.initials: CC
authors.lastname: Sun
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D004574:Electromagnetic Fields; D004583:Electrons; D006851:Hydrochloric Acid / Q000737:chemistry*; D008956:Models, Chemical; D011522:Protons; D014867:Water / Q000737:chemistry*
chemical_list: D011522:Protons; D014867:Water; D000641:Ammonia; D006851:Hydrochloric Acid