Cited Article: Maibaum, L. A coarse-grained model of water confined in a hydrophobic tube
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Title:
Coaxial Cross-Diffusion through Carbon Nantoubes
Authors:
Rodriguez, J; Elola, MD; Laria, D
Author Full Names:
Rodriguez, Javier; Dolores Elola, M.; Laria, Daniel
Source:
JOURNAL OF PHYSICAL CHEMISTRY B 113 (45): 14844-14848 NOV 12 2009
Language:
English
Document Type:
Article
KeyWords Plus:
MOLECULAR-DYNAMICS SIMULATIONS; NANOTUBE MEMBRANES; LIQUID WATER; TRANSPORT; MIXTURES; PORES; MODEL
Abstract:
We present results from nonequilibrium molecular dynamics experiments describing the relaxation of local concentrations at two reservoirs, initially filled with water (W) and acetonitrile (ACN), as they become connected through a membrane composed of (16,16) carbon nanotubes. Within the hydrophobic nanotube cavities, the equilibrium concentrations contrast sharply to those observed at the reservoirs, with a clear enhancement of ACN, in detriment of W. From the dynamical side, the relaxation involves three well-differentiated stages; the first one corresponds to the equilibration of individual concentrations within the nanotubes. An intermediate interval with Fickian characteristics follows, during which the overall transport can be cast in terms of coaxial opposite fluxes, with a central water domain segregated from an external ACN shell, in close contact with the tube walls. We also found evidence of a third, much slower, mechanism to reach equilibration, which involves str!
uctural modifications of tightly bound solvation shells, in close contact with the nanotube rims.
Reprint Address:
Laria, D, Comis Nacl Energia Atom, Dept Fis, Ave Libertador 8250, RA-1429 Buenos Aires, DF, Argentina.
Research Institution addresses:
[Rodriguez, Javier; Dolores Elola, M.; Laria, Daniel] Comis Nacl Energia Atom, Dept Fis, RA-1429 Buenos Aires, DF, Argentina; [Rodriguez, Javier] UNSAM, ECyT, RA-1650 San Martin, Buenos Aires, Argentina; [Laria, Daniel] Univ Buenos Aires, Dept Quim Inorgan Analit & Quim Fis & INQUIMAE, Fac Ciencias Exactas & Nat, RA-1428 Buenos Aires, DF, Argentina
E-mail Address:
dhlaria@cnea.gov.ar
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Cited Reference Count:
47
Times Cited:
0
Publisher:
AMER CHEMICAL SOC; 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Subject Category:
Chemistry, Physical
ISSN:
1520-6106
DOI:
10.1021/jp908791b
IDS Number:
514WY
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Title:
Vibrational Spectroscopy and Dynamics of Water Confined inside Reverse Micelles
Authors:
Pieniazek, PA; Lin, YS; Chowdhary, J; Ladanyi, BM; Skinner, JL
Author Full Names:
Pieniazek, Piotr A.; Lin, Yu-Shan; Chowdhary, Janamejaya; Ladanyi, Branka M.; Skinner, J. L.
Source:
JOURNAL OF PHYSICAL CHEMISTRY B 113 (45): 15017-15028 NOV 12 2009
Language:
English
Document Type:
Review
KeyWords Plus:
ULTRAFAST INFRARED-SPECTROSCOPY; HYDROGEN-BOND DYNAMICS; PROTEIN HYDRATION WATER; MOLECULAR-DYNAMICS; SOLVATION DYNAMICS; LIQUID WATER; COMPUTER-SIMULATION; NEUTRON-SCATTERING; SPECTRAL DIFFUSION; NMR-SPECTROSCOPY
Abstract:
In this work, we combine atomistic molecular dynamics simulations with theoretical vibrational spectroscopy to study the properties of water confined inside bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles. This approach is found to successfully reproduce the experimental spectra, rotational anisotropy decays, and spectral diffusion time-correlation functions as a function of micelle size. These results are interpreted in terms of water molecules in different hydrogen bonding environments. One interesting result from our simulation, not directly accessible experimentally, involves the distance from the surfactant headgroup/water interface over which the dynamical properties of water become bulk-like. We find that this distance varies with micelle size, casting doubt on the core/shell model. In particular, the distance increases with decreasing micelle size, and hence decreasing radius of curvature of the interface. We suggest that this arises from curvature-induced fru!
stration. We also find that the dynamics in the smallest micelle studied is extremely slow-relaxation is still incomplete by 1 ns. As in other glassy systems with collective relaxation, our time-correlation functions can be fit to stretched exponentials, in this case with very small exponents.
Reprint Address:
Skinner, JL, Univ Wisconsin, Inst Theoret Chem, Madison, WI 53706 USA.
Research Institution addresses:
[Pieniazek, Piotr A.; Lin, Yu-Shan; Skinner, J. L.] Univ Wisconsin, Inst Theoret Chem, Madison, WI 53706 USA; [Pieniazek, Piotr A.; Lin, Yu-Shan; Skinner, J. L.] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA; [Chowdhary, Janamejaya; Ladanyi, Branka M.] Colorado State Univ, Dept Chem, Ft Collins, CO 80523 USA
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Cited Reference Count:
159
Times Cited:
0
Publisher:
AMER CHEMICAL SOC; 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Subject Category:
Chemistry, Physical
ISSN:
1520-6106
DOI:
10.1021/jp906784t
IDS Number:
514WY
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