Vibrational and orientational relaxation of polyatomic anions and ion-molecular hydrogen bond in aqueous solutions

Perelygin, I. S.; Mikhailov, G.P.; Tuchkov, S. V.

doi:10.1016/0022-2860(95)09194-7

Cited by 11 publications

(12 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our calculations show a significantly faster rotational relaxation of water in the hydration shell of the nitrate ion which is in agreement with earlier experimental results. 16,34,74 As the hydrogen bonds get weaker, the OD frequency is blue-shifted and the reorientation of water molecules becomes faster in the solvation shell than that in the bulk. The nitrate ion−water hydrogen bond lifetime is also found to be shorter than that of water−water hydrogen bonds.…”

Section: Discussionmentioning

confidence: 99%

A First-Principles Molecular Dynamics Study of the Solvation Shell Structure, Vibrational Spectra, Polarity, and Dynamics around a Nitrate Ion in Aqueous Solution

2017

View full text Add to dashboard Cite

A first-principles molecular dynamics study is presented for the structural, dynamical, vibrational, and dipolar properties of the solvation shell of a nitrate ion in deuterated water. A detailed description of the anisotropic structure of the solvation shell is presented through calculations of various structural distributions in different conical shells around the perpendicular axis of the ion. The nitrate ion-water dimer potential energies are also calculated for many different orientations of water. The average vibrational stretch frequency of OD modes in the solvation shell is found to be higher than that of other OD modes in the bulk, which signifies a weakening of hydrogen bonds in the hydration shell. A splitting of the NO stretch frequencies and an associated fast spectral diffusion of the solute are also observed in the current study. The dynamics of rotation and hydrogen bond relaxation are found to be faster in the hydration shell than that in the bulk water. The residence time of water in the hydration shell is, however, found to be rather long. The nitrate ion is found to have a dipole moment of 0.9 D in water which can be attributed to its fluctuating interactions with the surrounding water.

show abstract

Section: Discussionmentioning

confidence: 99%

A First-Principles Molecular Dynamics Study of the Solvation Shell Structure, Vibrational Spectra, Polarity, and Dynamics around a Nitrate Ion in Aqueous Solution

2017

View full text Add to dashboard Cite

show abstract

“…22 Here we use 2D-IR and pump-probe spectroscopy to investigate the fluctuations in the ion-water hydrogen bonds, the intra-molecular coupling of the vibrational modes of nitrate and the reorientation of the nitrate molecules. A similar approach was recently taken by Hochstrasser and co-workers, who investigated the water-induced relaxation of Guanidinium (D 3 -symmetry).…”

Section: Introductionmentioning

confidence: 99%

Hydration Dynamics of Aqueous Nitrate

et al. 2013

View full text Add to dashboard Cite

Aqueous nitrate, NO3-(aq), was studied by 2D-IR, UV-IR, and UV-UV time-resolved spectroscopies in combination with molecular dynamics (MD) simulations with the purpose of determining the hydration dynamics around the anion. In water, the D3h symmetry of NO3-is broken, and the degeneracy of the asymmetric-stretch modes is lifted. This provides a very sensitive probe of the ionwater interactions. The 2D-IR measurements reveal excitation exchange between the two nondegenerate asymmetric-stretch vibrations on a 300-fs time scale concomitant with fast anisotropy decay of the diagonal-peak signals. The MD simulations show that this is caused by jumps of the transition dipole orientations related to fluctuations of the hydrogen bonds connecting the nitrate ion to the nearest water molecules. Reorientation of the ion, which is associated with the hydrogen-bond breaking, was monitored by time-resolved UV-IR and UV-UV spectroscopy, revealing a 2-ps time constant. These time scales are very similar to those reported for isotope-labeled water, suggesting that NO3-(aq) has a labile hydration shell. connecting the nitrate ion to the nearest water molecules. Reorientation of the ion, which is associated with the hydrogen bond breaking, is monitored by time resolved UV-IR-and UV-UV spectroscopy, revealing a 2 ps time constant. These time scales are very similar to those reported for isotope-labeled water, suggesting that NO 3¯( aq) has a labile hydration shell.

show abstract

“…Compared with the monovalent ions of the same centration C, the Z 2+ and 2Xin a divalent salt solution "hardens" drinking water and they are harmful to living creatures [33,34]. From the perspective of classical thermodynamics, namely, the density, isothermal compressibility, and surface tension, a coarse-grained electrolyte solution model was proposed, being capable of reproducing some trends on how salts influence the diffusivity and viscosity of the solutions [35,36].…”

Section: Concurrent Status and Known Factsmentioning

confidence: 99%