Attosecond Charge Migration with TDDFT: Accurate Dynamics from a Well-Defined Initial State

被引：75

作者：

Bruner, Adam ^{[1
]}

Hernandez, Samuel ^{[1
]}

Mauger, Francois ^{[2
]}

Abanador, Paul M. ^{[2
]}

LaMaster, Daniel J. ^{[1
]}

Gaarde, Mette B. ^{[2
]}

Schafer, Kenneth J. ^{[2
]}

Lopata, Kenneth ^{[1
,3
]}

机构：

[1] Louisiana State Univ, Dept Chem, Baton Rouge, LA 70803 USA

[2] Louisiana State Univ, Dept Phys & Astron, Baton Rouge, LA 70803 USA

[3] Louisiana State Univ, Ctr Computat & Technol, Baton Rouge, LA 70803 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2017年 / 8卷 / 17期

关键词：

DENSITY-FUNCTIONAL THEORY; TRANSFER EXCITED-STATES; DOUBLE-EXCITATION CHARACTER; SELF-INTERACTION ERROR; ELECTRON LOCALIZATION; BASIS-SETS; MOLECULES; APPROXIMATION; SPECTROSCOPY; IONIZATION;

D O I：

10.1021/acs.jpclett.7b01652

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 investigate the ability of time-dependent density functional theory (TDDFT) to capture attosecond valence electron dynamics resulting from sudden X-ray ionization of a core electron. In this special case the initial state can be constructed unambiguously, allowing for a simple test of the accuracy of the dynamics. The response following nitrogen K-edge ionization in nitrosobenzene shows excellent agreement with fourth order algebraic diagrammatic construction (ADC(4)) results, suggesting that a properly chosen initial state allows TDDFT to adequately capture attosecond charge migration. Visualizing hole motion using an electron localization picture (ELF), we provide an intuitive chemical interpretation of the charge migration as a superposition of Lewis dot resonance structures.

引用

页码：3991 / 3996

页数：6

共 69 条

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