TY - JOUR
T1 - Molecular theory on dielectric constant at interfaces
T2 - A molecular dynamics study of the water/vapor interface
AU - Shiratori, Kazuya
AU - Morita, Akihiro
N1 - Funding Information:
The present work has been supported by the Global COE Project, Next Generation Supercomputer Project, and Grants-in-Aid by the Ministry of Education, Cultures, Supports, Science and Technology (MEXT), Japan. The computations were carried out at Information Technology Center, the University of Tokyo.
PY - 2011/6/21
Y1 - 2011/6/21
N2 - Though the local dielectric constant at interfaces is an important phenomenological parameter in the analysis of surface spectroscopy, its microscopic definition has been uncertain. Here, we present a full molecular theory on the local field at interfaces with the help of molecular dynamics simulation, and thereby provide microscopic basis for the local dielectric constant so as to be consistent to the phenomenological three-layer model of interface systems. To demonstrate its performance, we applied the theory to the water/vapor interface, and obtained the local field properties near the interface where the simple dielectric model breaks down. Some computational issues pertinent to Ewald calculations of the dielectric properties are also discussed.
AB - Though the local dielectric constant at interfaces is an important phenomenological parameter in the analysis of surface spectroscopy, its microscopic definition has been uncertain. Here, we present a full molecular theory on the local field at interfaces with the help of molecular dynamics simulation, and thereby provide microscopic basis for the local dielectric constant so as to be consistent to the phenomenological three-layer model of interface systems. To demonstrate its performance, we applied the theory to the water/vapor interface, and obtained the local field properties near the interface where the simple dielectric model breaks down. Some computational issues pertinent to Ewald calculations of the dielectric properties are also discussed.
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U2 - 10.1063/1.3598484
DO - 10.1063/1.3598484
M3 - Article
AN - SCOPUS:79959742276
SN - 0021-9606
VL - 134
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 23
M1 - 234705
ER -