Disentanglement of triplet and singlet states of azobenzene: direct EELS detection and QMC modeling

被引：21

作者：

Dubecky, M. ^{[1
]}

Derian, R. ^{[1
]}

Horvathova, L. ^{[1
]}

Allan, M. ^{[2
]}

Stich, I. ^{[1
]}

机构：

[1] Slovak Acad Sci, Inst Phys, Ctr Computat Mat Sci, Bratislava 84511, Slovakia

[2] Univ Fribourg, Dept Chem, CH-1700 Fribourg, Switzerland

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2011年 / 13卷 / 47期

基金：

瑞士国家科学基金会;

关键词：

QUANTUM MONTE-CARLO; LOWEST ELECTRONIC STATES; CIS-TRANS ISOMERIZATION; AB-INITIO CALCULATION; WAVE-FUNCTIONS; PHOTOISOMERIZATION; SPECTRA; ABSORPTION; SPECTROSCOPY; SIMULATIONS;

D O I：

10.1039/c1cp22520k

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：

Singlet and triplet excited states of trans-azobenzene have been measured in the gas phase by electron energy loss spectroscopy (EELS). In order to interpret the strongly overlapping singlet and triplet bands in the spectra a set of large-scale correlated quantum Monte-Carlo (QMC) simulations was performed. The EELS/QMC combination of methods yields an excellent agreement between theory and experiment and for the two low-lying excited singlet and two low-lying triplet states permitted their unambiguous assignment. In addition, EELS revealed two overlapping electronic states in the band commonly assigned as S-2, the lower one with a pronounced vibrational structure, the upper one structureless. Finally, the agreement between theory and experiment was shown to further increase by taking computationally into account the finite temperature effects.

引用

页码：20939 / 20945

页数：7

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