title: Comparison of cationic, anionic and neutral hydrogen bonded dimers.
abstract: Short Strong Hydrogen Bonds (SSHBs) play an important role in many fields of physics, chemistry and biology. Since it is known that SSHBs exist in many biological systems, the role of hydrogen bonding motifs has been particularly interesting in enzyme catalysis, bio-metabolism, protein folding and proton transport phenomena. To explore the characteristic features of neutral, anionic and cationic hydrogen bonds, we have carried out theoretical studies of diverse homogeneous and heterogeneous hydrogen bonded dimers including water, peroxides, alcohols, ethers, aldehydes, ketones, carboxylic acids, anhydrides, and nitriles. Geometry optimization and harmonic frequency calculations are performed at the levels of Density Functional Theory (DFT) and Møller-Plesset second order perturbation (MP2) theory. First principles Car-Parrinello molecular dynamics (CPMD) simulations are performed to obtain IR spectra derived from velocity- and dipole-autocorrelation functions. We find that the hydrogen bond energy is roughly inversely proportional to the fourth power of the r(O/N-H) distance. Namely, the polarization of the proton accepting O/N atom by the proton-donating H atom reflects most of the binding energy in these diverse cation/anion/neutral hydrogen bonds. The present study gives deeper insight into the nature of hydrogen-bonded dimers including SSHBs.
authors.affiliation: Center for Superfunctional Materials, Department of Chemistry, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, 790-784 Pohang, South Korea.
authors.forename: Han Myoung
authors.initials: HM
authors.lastname: Lee
authors.forename: Anupriya
authors.initials: A
authors.lastname: Kumar
authors.forename: Maciej
authors.initials: M
authors.lastname: Kołaski
authors.forename: Dong Young
authors.initials: DY
authors.lastname: Kim
authors.forename: Eun Cheol
authors.initials: EC
authors.lastname: Lee
authors.forename: Seung Kyu
authors.initials: SK
authors.lastname: Min
authors.forename: Mina
authors.initials: M
authors.lastname: Park
authors.forename: Young Cheol
authors.initials: YC
authors.lastname: Choi
authors.forename: Kwang S
authors.initials: KS
authors.lastname: Kim
mesh_terms: D000838:Anions / Q000737:chemistry*; D002412:Cations / Q000737:chemistry*; D019281:Dimerization; D006860:Hydrogen Bonding; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics
chemical_list: D000838:Anions; D002412:Cations