Deprotonated sulfamic acid and its homodimers: Does sulfamic acid adopt zwitterion during cluster growth?

ABSTRACT

We present a joint experimental and computational study on the geometric and electronic structures of deprotonated sulfamic acid (SA) clusters [(SA)n-H]- (n = 1, 2) employing negative ion photoelectron spectroscopy and high-level ab initio calculations. The photoelectron spectra provide the vertical/adiabatic detachment energy (VDE/ADE) of the sulfamate anion (SM-) H2N●SO3- at 4.85 ± 0.05 and 4.58 ± 0.08 eV, respectively, and the VDE and ADE of the SM-●SA dimer at 6.41 ± 0.05 and 5.87 ± 0.08 eV, respectively. The significantly increased electron binding energies of the dimer confirm the enhanced electronic stability upon the addition of one SA molecule. The CCSD(T)-predicted VDEs/ADEs agree excellently with the experimental data, confirming the identified structures as the most stable ones. Two types of dimer isomers possessing different hydrogen bonding (HB) motifs are identified, corresponding to SM- binding to a zwitterionic SA (SM-●SAz) and a canonical SA (SM-●SAc), respectively. Two N-H⋯O HBs and one superior O-H⋯O HB are formed in the lowest-lying SM-●SAc, while SM-●SAz has three moderate N-H⋯O HBs, with the former being 4.71 kcal/mol more stable. Further theoretical analyses reveal that the binding strength advantage of SM-●SAc over SM-●SAz arises from its significant contributions of orbital interactions between fragments, illustrating that sulfamate strongly interacts with its parent SA acid and preferably chooses the canonical SA in the subsequent cluster formations. Given the prominent presence of SA, this study provides the first evidence that the canonical dimer model of sulfamic acid should exist as a superior configuration during cluster growth.