When an ion transports from water to oil through water-oil interface, it accompanies hydrated water molecules and transiently forms a chain of water, called “water finger.” We thoroughly investigated the role of the water finger in chloride ion transport through water-dichloromethane interface by using molecular dynamics technique. We developed a proper coordinate w to describe the water finger structure and calculated the free energy landscape and the friction for the ion transport as a function of ion position z and the water finger coordinate w. It is clearly shown that the formation and break of water finger accompanies an activation barrier for the ion transport, which has been overlooked in the conventional free energy curve along the ion position z. The present analysis of the friction does not support the hypothesis of augmented local friction (reduced local diffusion coefficient) at the interface. These results mean that the experimentally observed rate constants of interfacial ion transfer are reduced from the diffusion-limited one because of the activation barrier associated to the water finger, not the anomalous local diffusion. We also found that the nascent ion just after the break of water finger has excessive hydration water than that in the oil phase.
REFERENCES
1.
H.
Freiser
, Chem. Rev.
88
, 611
–616
(1988
).2.
J.
de Gyves
and E.
Rodríguez de San Miguel
, Ind. Eng. Chem. Res.
38
, 2182
–2202
(1999
).3.
C. M.
Starks
, M.
Halpern
, and C. L.
Liotta
, Phase-Transfer Catalysis: Fundamentals, Applications, and Industrial Perspectives
(Chapman & Hall
, 1994
).4.
H. H.
Girault
, Electroanalytical Chemistry: A series of Advances
(CRC Press
, 2010
), Vol. 23
, pp. 1
–104
.5.
P.
Läuger
and G.
Stark
, Biochim. Biophys. Acta, Biomembr.
211
, 458
–466
(1970
).6.
C. E.
Kolb
, R. A.
Cox
, J. P. D.
Abbatt
, M.
Ammann
, E. J.
Davis
, D. J.
Donaldson
, B. C.
Garrett
, C.
George
, P. T.
Griffiths
, D. R.
Hanson
, M.
Kulmala
, G.
McFiggans
, U.
Pöschl
, I.
Riipinen
, M. J.
Rossi
, Y.
Rudich
, P. E.
Wagner
, P. M.
Winkler
, D. R.
Worsnop
, and C. D.
O’Dowd
, Atmos. Chem. Phys.
10
, 10561
–10605
(2010
).7.
Z.
Samec
, Electrochim. Acta
84
, 21
–28
(2012
).8.
S.
Amemiya
, J.
Kim
, A.
Izadyar
, B.
Kabagambe
, M.
Shen
, and R.
Ishimatsu
, Electrochim. Acta
110
, 836
–845
(2013
).9.
B. R.
Silver
, K.
Holub
, and V.
Marecek
, J. Electroanal. Chem.
731
, 107
–111
(2014
).10.
Y.
Wang
, J.
Velmurugan
, M. V.
Mirkin
, P. J.
Rodgers
, J.
Kim
, and S.
Amemiya
, Anal. Chem.
82
, 77
–83
(2010
).11.
R. A.
Marcus
, J. Chem. Phys.
113
, 1618
–1629
(2000
).12.
A.
Nitzan
, Chemical Dynamics in Condensed Phases
(Oxford University Press
, Oxford
, 2006
).13.
H. A.
Kramers
, Physica
7
, 284
–304
(1940
).14.
P.
Hänggi
, P.
Talkner
, and M.
Borkovec
, Rev. Mod. Phys.
62
, 251
–341
(1990
).15.
R. F.
Grote
and J. T.
Hynes
, J. Chem. Phys.
73
, 2715
–2732
(1980
).16.
L. X.
Dang
, J. Phys. Chem. B
103
, 8195
–8200
(1999
).17.
K.
Schweighofer
and I.
Benjamin
, J. Phys. Chem. A
103
, 10274
–10279
(1999
).18.
L. X.
Dang
, J. Phys. Chem. B
105
, 804
–809
(2001
).19.
D. J.
dos Santos
and J. A.
Gomes
, ChemPhysChem
3
, 946
–951
(2002
).20.
G.
Luo
, S.
Malkova
, J.
Yoon
, D. G.
Schultz
, B.
Lin
, M.
Meron
, I.
Benjamin
, P.
Vanysek
, and M. L.
Schlossman
, Science
311
, 216
–218
(2006
).21.
G.
Luo
, S.
Malkova
, J.
Yoon
, D. G.
Schultz
, B.
Lin
, M.
Meron
, I.
Benjamin
, P.
Vanýsek
, and M. L.
Schlossman
, J. Electroanal. Chem.
593
, 142
–158
(2006
).22.
C. D.
Wick
and L. X.
Dang
, J. Phys. Chem. C
112
, 647
–649
(2008
).23.
I.
Benjamin
, J. Phys. Chem. B
117
, 4325
–4331
(2013
).24.
N.
Kikkawa
, T.
Ishiyama
, and A.
Morita
, Chem. Phys. Lett.
534
, 19
–22
(2012
).25.
M.
Darvas
, M.
Jorge
, M. N.
Cordeiro
, S. S.
Kantorovich
, M.
Sega
, and P.
Jedlovszky
, J. Phys. Chem. B
117
, 16148
–16156
(2013
).26.
A.
Gupta
, A.
Chauhan
, and D. I.
Kopelevich
, Phys. Rev. E
78
, 041605
(2008
).27.
L.
Benjamin
, Science
261
, 1558
–1560
(1993
).28.
K. J.
Schweighofer
and I.
Benjamin
, J. Phys. Chem.
99
, 9974
–9985
(1995
).29.
A. A.
Kornyshev
, A. M.
Kuznetsov
, and M.
Urbakh
, J. Chem. Phys.
117
, 6766
–6779
(2002
).30.
L. I.
Daikhin
, A. A.
Kornyshev
, A. M.
Kuznetsov
, and M.
Urbakh
, Chem. Phys.
319
, 253
–260
(2005
).31.
I.
Benjamin
, J. Chem. Phys.
97
, 1432
–1445
(1992
).32.
D. P.
Tieleman
, S. J.
Marrink
, and H. J. C.
Berendsen
, Biochim. Biophys. Acta, Biomembr.
1331
, 235
–270
(1997
).33.
M.
Lauterbach
, E.
Engler
, N.
Muzet
, L.
Troxler
, and G.
Wipff
, J. Phys. Chem. B
102
, 245
–256
(1998
).34.
P.
Sun
, F. O.
Laforge
, and M. V.
Mirkin
, J. Am. Chem. Soc.
129
, 12410
–12411
(2007
).35.
K. V.
Nelson
and I.
Benjamin
, J. Phys. Chem. C
115
, 2290
–2296
(2011
).36.
N.
Kikkawa
, L.
Wang
, and A.
Morita
, J. Am. Chem. Soc.
137
, 8022
–8025
(2015
).37.
B.
Korte
and J.
Vygen
, Combinatorial Optimization: Theory and Algorithms
(Springer
, 2014
).38.
M. P.
Allen
and D. J.
Tildesley
, Computer Simulation of Liquids
(Oxford University Press
, 1989
).39.
Y.
Sugita
, A.
Kitao
, and Y.
Okamoto
, J. Chem. Phys.
113
, 6042
–6051
(2000
).40.
A.
Bowyer
, Comput. J.
24
, 162
–166
(1981
).41.
D. F.
Watson
, Comput. J.
24
, 167
–172
(1981
).42.
R.
Seidel
, Comput. Geom.
5
, 115
–116
(1995
).43.
H. C.
Andersen
, J. Comput. Phys.
52
, 24
–34
(1983
).44.
Y.
Sugita
and Y.
Okamoto
, Chem. Phys. Lett.
329
, 261
–270
(2000
).45.
N.
Metropolis
, A. W.
Rosenbluth
, M. N.
Rosenbluth
, A. H.
Teller
, and E.
Teller
, J. Chem. Phys.
21
, 1087
–1092
(1953
).46.
M.
Toda
, R.
Kubo
, N.
Saitō
, and N.
Hashitsume
, Statistical Physics II: Nonequilibrium Statistical Mechanics
(Springer Science & Business Media
, 1992
).47.
J.-P.
Ryckaert
, G.
Ciccotti
, and H. J. C.
Berendsen
, J. Comput. Phys.
23
, 327
–341
(1977
).48.
S.
Nosé
, J. Chem. Phys.
81
, 511
(1984
).49.
W. G.
Hoover
, Phys. Rev. A
31
, 1695
–1697
(1985
).50.
W. C.
Swope
, H. C.
Andersen
, P. H.
Berens
, and K. R.
Wilson
, J. Chem. Phys.
76
, 637
–649
(1982
).51.
J. W.
Caldwell
and P. A.
Kollman
, J. Phys. Chem.
99
, 6208
–6219
(1995
).52.
H. A.
Lorentz
, Ann. Phys.
248
, 127
–136
(1881
).53.
54.
F. J.
Vesely
, J. Comput. Phys.
24
, 361
–371
(1977
).55.
W. H.
Press
, Numerical Recipes 3rd Edition: The Art of Scientific Computing
(Cambridge University Press
, 2007
).56.
Y.
Marcus
, Pure Appl. Chem.
55
, 977
–1021
(1983
).57.
S.
Sakaguchi
and A.
Morita
, J. Chem. Phys.
137
, 064701
(2012
).58.
C.
Gavach
, B.
D’Epenoux
, and F.
Henry
, J. Electroanal. Chem.
64
, 107
–115
(1975
).59.
Z.
Samec
and V.
Mareček
, J. Electroanal. Chem.
200
, 17
–33
(1986
).60.
L.
Yuan-Hui
and S.
Gregory
, Geochim. Cosmochim. Acta
38
, 703
–714
(1974
).61.
B. J.
Gertner
, K. R.
Wilson
, and J. T.
Hynes
, J. Chem. Phys.
90
, 3537
–3558
(1989
).62.
A.
Trojánek
, V.
Mareček
, and Z.
Samec
, Electrochim. Acta
180
, 366
–372
(2015
).63.
D.
Rose
and I.
Benjamin
, J. Phys. Chem. B
113
, 9296
–9303
(2009
).64.
I.
Benjamin
, J. Phys. Chem. B
112
, 15801
–15806
(2008
).65.
S.
Kusakabe
and M.
Arai
, Bull. Chem. Soc. Jpn.
69
, 581
–588
(1996
).66.
R. D.
Milne
, SIAM J. Appl. Math.
16
, 931
–944
(1968
).67.
C. R.
Rao
and S. K.
Mitra
, Generalized Inverse of Matrices and Its Applications
(Wiley
, New York
, 1971
).© 2016 Author(s).
2016
Author(s)
You do not currently have access to this content.
