The cavity electromagnetic field within the polarizable continuum model of solvation: An application to the real-time time dependent density functional theory

被引：21

作者：

Pipolo, Silvio ^{[1
]}

Corni, Stefano ^{[1
]}

Cammi, Roberto ^{[2
]}

机构：

[1] CNR Inst Nanosc, Ctr S3, Modena, Italy

[2] Univ Parma, Dept Chem, I-43100 Parma, Italy

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2014年 / 1040卷

关键词：

Cavity field effects; Polarizable continuum model; Real-time TDDFT; INFRARED INTENSITIES; VIBRATIONAL INTENSITIES; CIRCULAR-DICHROISM; OPTICAL-RESPONSE; LINEAR-RESPONSE; PURE LIQUIDS; BASIS-SETS; MOLECULES; RAMAN; ABSORPTION;

D O I：

10.1016/j.comptc.2014.02.035

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We present an extension of the cavity-field formulation for the Polarizable Continuum Model (PCM), to the Real-Time Time Dependent Density Functional Theory (RT-TDDFT). Both the length- and velocity-gauge formalisms are developed, through the approach based on effective dipole moment and momentum operators. We apply our formulation to the calculation of imaginary parts of the electric and mixed (electric-magnetic) polarizabilities, i.e. transition dipole moments and rotatory strengths for a model system, the twisted ethylene. To validate our approach we first compare the results obtained with the corresponding properties calculated within a PCM Linear-Response (LR) TDDFT formalism, and we check numerically the gauge-invariance of our formulation. Finally we also compare with the results of analytical models. (C) 2014 Elsevier B.V. All rights reserved.

引用

页码：112 / 119

页数：8

共 96 条

[1] Short-time Fourier transform analysis of real-time time-dependent Hartree-Fock and time-dependent density functional theory calculations with Gaussian basis functions [J].