Ab initio depolarization in self-assembled molecular monolayers: Beyond conventional density-functional theory

被引：24

作者：

Piacenza, M. ^{[1
]}

D'Agostino, S. ^{[1
]}

Fabiano, E. ^{[1
]}

Della Sala, F. ^{[1
]}

机构：

[1] Distretto Tecnol ISUFI, CNR, Natl Nanotechnol Lab INFM, I-73100 Lecce, Italy

来源：

PHYSICAL REVIEW B | 2009年 / 80卷 / 15期

基金：

欧洲研究理事会;

关键词：

EXACT-EXCHANGE; HARTREE-FOCK; ENERGY; SURFACE; MODEL; APPROXIMATION; DIPOLES; CC2;

D O I：

10.1103/PhysRevB.80.153101

中图分类号：

T [工业技术];

学科分类号：

08 ;

摘要：

We present an efficient ab initio atomic-orbital-based embedding scheme, which allows to describe depolarization effects in self-assembled organic monolayers (SAMs). The method includes periodic-boundary conditions, all multipole moments and local-field effects. Results for substituted oligophenyl SAM, in combination with conventional, hybrid and orbital-dependent density-functional theory (DFT) as well as coupled-cluster (CC) approach, are reported. We find that the accuracy of conventional DFT relies on error cancellation between the concurrent overestimation of dipole and polarizability, but it can yield quantitatively and sometimes even qualitatively wrong results. Hybrid and orbital-dependent functionals strongly improve the overall description and closely reproduce CC results.

引用

页数：4

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