Tuning the inter-molecular charge transfer, second-order nonlinear optical and absorption spectra properties of a π-dimer under an external electric field
In this work, we applied an external electric field (F) to a biphenalenyl derivative (BN-PLY ) in the direction of the negative z-axis (F ) and the positive z-axis (F ), respectively. The influence of the two directions of F on the molecular structures and electronic properties is investigated, whic...
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Published in | Physical chemistry chemical physics : PCCP Vol. 19; no. 47; pp. 31958 - 31964 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
England
Royal Society of Chemistry
2017
|
Subjects | |
Online Access | Get full text |
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Summary: | In this work, we applied an external electric field (F) to a biphenalenyl derivative (BN-PLY
) in the direction of the negative z-axis (F
) and the positive z-axis (F
), respectively. The influence of the two directions of F on the molecular structures and electronic properties is investigated, which gives interesting results. Density functional theory (DFT) calculations show that the application of F
(F
= 0 to -190 × 10
) is an advantage toward improving π-dimer stability, which is attributed to an increase in bonding and attractive electrostatic interactions. Interestingly, a large amount of negative charge is induced by applying F
to the upper layer, resulting in an increase in the electron density in the upper layer, which is the main factor for the formation of a symmetric highest occupied molecular orbital (HOMO) at F
= -180 × 10
au (-9.26 × 10
V m
). Moreover, when F
is applied, the HOMO and HOMO-1 undergo orbital interchange in the π-dimer at F
= 100/110 × 10
au. Significantly, the effect of the external electric field effectively regulates the first hyperpolarizabilities (β
). When the F
ranges from 0 to 140 × 10
au, the β
values slightly decrease to 0 au. Note that, upon increasing F
, the β
values sharply increase to 6.67 × 10
au (F
= 190 × 10
au). Furthermore, the evolutions of the absorption spectra under F might well explain the trend of β
values. When the F
ranges from 0 to 140 × 10
au, the broad absorption spikes with a low-energy are significantly blue-shifted, while only absorption spikes with a high-energy are significantly red-shifted (F
= 140 to 190 × 10
au). The present work not only provides a deeper understanding of the relationships between the molecular structure and the electronic properties of a π-dimer system, but can also be developed for designing highly efficient nonlinear optical materials through the influence of an external electric field. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1463-9076 1463-9084 |
DOI: | 10.1039/c7cp06412h |