We analyze the density correlations in a liquid-vapor surface to establish a quantitative connection between the Density Functional (DF) formalism, Molecular Dynamic (MD) simulations, and the Capillary Wave (CW) theory. Instead of the integrated structure factor, we identify the CW fluctuations as eigenmodes of the correlation function. The square-gradient DF approximation appears as fully consistent with the use of the thermodynamic surface tension to describe the surface fluctuations for any wavevector because it misses the upper cutoff in the surface Hamiltonian from the merging of the CW mode with the non-CW band. This mesoscopic cutoff may be accurately predicted from the main peak in the structure factor of the bulk liquid. We explore the difference between the full density-density correlation mode and the bare CW that represents the correlation between the corrugation of the intrinsic surface and the density at the interfacial region. The non-local decay of the CW effects, predicted from DF analysis and observed in MD simulations with the intrinsic sampling method, is found to characterize the bare CW fluctuations, which also require a wavevector-dependent surface tension.

1.
F. P.
Buff
,
R. A.
Lovett
, and
F. H.
Stillinger
,
Phys. Rev. Lett.
15
,
621
(
1965
).
2.
R.
Evans
,
Adv. Phys.
28
,
143
(
1979
).
3.
J. K.
Percus
and
G.
Williams
, in
Fluid Interfacial Phenomena
, edited by
C.
Croxton
(
John Wiley
,
New York
,
1986
), pp.
1
44
.
4.
P. S.
Pershan
,
Colloids Surf., A
171
,
149
(
2000
).
5.
P. S.
Pershan
,
J. Phys. Chem. B
113
,
3639
(
2009
).
6.
S.
Mora
,
J.
Daillant
,
K. R.
Mecke
,
D.
Luzet
,
A.
Braslau
,
M.
Alba
, and
B.
Struth
,
Phys. Rev. Lett.
90
,
216101
(
2003
).
7.
D. X.
Li
,
B.
Yang
,
B. H.
Lin
,
M.
Meron
,
J.
Gebhardt
,
T.
Graber
, and
S. A.
Rice
,
Phys. Rev. Lett.
92
,
136102
(
2004
).
8.
F.
Höfling
and
S.
Dietrich
,
Europhys. Lett.
109
,
46002
(
2015
).
9.
F.
Sedlmeier
,
D.
Horinek
, and
R.
Netz
,
Phys. Rev. Lett.
103
,
136102
(
2009
).
10.
E.
Chacón
and
P.
Tarazona
,
J. Phys.: Condens. Matter
117
(
45
),
S3493
(
2005
).
11.
M.
Napiórkowski
and
S.
Dietrich
,
Phys. Rev. E
47
,
1836
(
1993
).
12.
S.
Dietrich
and
M.
Napiórkowski
,
Phys. Rev. A
43
,
1861
(
1991
).
13.
K. R.
Mecke
and
S.
Dietrich
,
Phys. Rev. E
59
,
6766
(
1999
).
14.
E. M.
Blokhuis
,
J.
Kuipers
, and
R. L. C.
Vink
,
Phys. Rev. Lett.
101
,
086101
(
2008
).
15.
E. M.
Blokhuis
,
J. Chem. Phys.
130
,
014706
(
2009
).
16.
E.
Chacón
and
P.
Tarazona
,
J. Phys.: Condens. Matter
28
,
244014
(
2016
).
17.
E.
Tarazona
,
P.
Chacón
, and
F.
Bresme
,
J. Phys.: Condens. Matter
24
,
284123
(
2012
).
18.
J.
Stecki
,
J. Chem. Phys.
107
,
7967
(
1997
).
19.
A. O.
Parry
,
C.
Rascón
,
G.
Willis
, and
R.
Evans
,
J. Phys.: Condens. Matter
26
,
355008
(
2014
).
20.
A. O.
Parry
,
C.
Rascon
, and
R.
Evans
,
Phys. Rev. E
91
,
030401(R)
(
2015
).
21.
J.
Hernández-Muñoz
,
E.
Chacón
, and
P.
Tarazona
,
Phys. Rev. E
94
,
062802
(
2016
).
22.
J.
Zittartz
,
Phys. Rev.
154
,
529
(
1967
).
23.
M. S.
Wertheim
,
J. Chem. Phys.
65
,
2377
(
1976
).
24.
E.
Chacón
and
P.
Tarazona
,
Phys. Rev. Lett.
91
,
166103
(
2003
).
25.
F.
Bresme
,
E.
Chacón
, and
P.
Tarazona
,
Phys. Chem. Chem. Phys.
10
,
4704
(
2008
).
26.
P.
Tarazona
and
E.
Chacón
,
Phys. Rev. B
70
,
235407
(
2004
).
27.
E.
Chacón
,
E. M.
Fernández
,
D.
Duque
,
R.
Delgado-Buscalioni
, and
P.
Tarazona
,
Phys. Rev. B
80
,
195403
(
2009
).
28.
S.
Plimpton
,
J. Comput. Phys.
117
,
1
(
1995
).
29.
F. H.
Stillinger
,
J. Chem. Phys.
76
,
1087
(
1982
).
30.
F. H.
Stillinger
and
J.
Weeks
,
J. Chem. Phys.
99
,
2807
(
1995
).
31.
M.
Jorge
,
G.
Hantal
,
P.
Jedlovszky
, and
N.
Cordeiro
,
J. Phys. Chem. C
114
,
18656
(
2010
).
32.
A.
Willard
and
D.
Chandler
,
J. Phys. Chem. B
114
,
1954
(
2010
).
33.
D.
Zhukhovitskii
,
J. Chem. Phys.
125
,
234701
(
2006
).
34.
R.
Delgado-Buscalioni
,
E.
Chacón
, and
P.
Tarazona
,
Phys. Rev. Lett.
101
,
106102
(
2008
).
35.
A. O.
Parry
,
C.
Rascón
,
N. R.
Bernardino
, and
J. M.
Romero-Enrique
,
J. Phys.: Condens. Matter
18
,
6433
(
2006
).
36.
A. O.
Parry
,
C.
Rascón
,
N.
Bernardino
, and
J.
Romero-Enrique
,
J. Phys.: Condens. Matter
19
,
416105
(
2007
).
37.
A. O.
Parry
,
C.
Rascón
, and
R.
Evans
,
J. Phys.: Condens. Matter
28
,
244013
(
2016
).
38.
E. M.
Fernández
,
E.
Chacón
,
P.
Tarazona
,
A. O.
Parry
, and
C.
Rascón
,
Phys. Rev. Lett.
111
,
096104
(
2013
).
39.
E.
Chacón
,
E. M.
Fernández
, and
P.
Tarazona
,
Phys. Rev. E
89
,
042406
(
2014
).
You do not currently have access to this content.