Can Water Polarizability Be Ignored in Hydrogen Bond Kinetics?
نویسندگان
چکیده
The kinetics of forming and breaking water-water hydrogen bonds in neat water, an aqueous solution of ethane, and an aqueous solution of NaCl are studied by molecular dynamics simulations. We compare nonpolarizable and polarizable water models to elucidate the effect of water’s polarizability on hydrogen bonds. We find that polarizability strengthens the hydrogen bonds and increases the hydrogen bond relaxation time by a factor of between 50% and 100%. The Gibbs energy of activation for breaking hydrogen bonds is ∼0.2 kcal‚mol-1 higher for the polarizable water model. Polarizability also causes the rate of forming and breaking hydrogen bonds to be more dependent on the local environment.
منابع مشابه
Distributed polarizability of the water dimer: Field-induced charge transfer along the hydrogen bond
The topological partitioning of electronic properties approach at Hartree-Fock level is used to investigate charge transfer response in a water dimer. Distributed polarizability components are employed to calculate the change in electron density under external fields. Field-induced charge flow between the water monomers is most significant along the direction of the hydrogen bond. The molecular...
متن کاملSolvent Effects on Complexation of Dioxovanadium (V) with Glycine in Methanol-Water Mixtures
The formation constants of the species formed in the systems fr + glycine + dioxovanadium(V) + and H+ + glycine have been determined in aqueous solutions of methanol at 25 °C and constant ionicstrength, using spectrophotometric and potentiometric techniques. It was shown thatdioxovanadium(V) forms two mononuclear 1 : land 1:2 complexes with glycine. The formationconstants in various media were ...
متن کاملBonding Properties of the Water Dimer: A Comparative Study of Density Functional Theories
For a variety of density functional theories, we examined the ground-state properties of the water monomer (geometry, vibrational frequencies, dipole moment, polarizability) and dimer (geometry, vibrational frequencies, bond energy, and barrier heights for the transition states for the interchange of hydrogen atoms within the dimer). Thus, we considered LDA (SVWN), seven pure GGA methods (BLYP,...
متن کاملDFT-PBE, DFT-D, and MP2 Studies on the H2O•••HNH and HOH•••NH2 Hydrogen Bonds in Water-Aniline Complexes
DFT-GGA method of Perdew-Burke-Ernzerhof (PBE) is used with aug-cc-PVTZ, 6-311++G**, and Def2-TZVP large basis sets to study the hydrogen bond interactions between oxygen lone pair as a donor electron with hydrogen atom connected to the aniline’s nitrogen as an electron acceptor (H2O···HNH-Ph), and nitrogen lone pair with hydrogen of water molecule (Ph-H2N···HOH...
متن کاملThe influence of chlorinated aromatics' structure on their adsorption characteristics on activated carbon to tackle chemical spills in drinking water source
This study focused on evaluating the efficiency of powdered activated carbon (PAC) adsorption process and tackling chlorobenzenes and chlorophenols spill in drinking water source. The adsorption kinetics and PAC’s capacities for five chlorobenzenes and three chlorophenols at drinking water contamination levels were studied in order to determine the influence of different functional groups on th...
متن کامل