Giant Enhancement of the Second Hyperpolarizabilities of Open-Shell Singlet Polyaromatic Diphenalenyl Diradicaloids by an External Electric Field and Donor–Acceptor Substitution

By doping two potassium atoms among three CF cages, peanut-shaped single molecular solvated dielectron (CF)&K was theoretically presented. The triplet structures with two excess electrons individually inside left and middle cages (isomers I or II) are thermodynamically more stable than both open-shell (OS) and close-shell (CS) singlet ones with lone pair of excess electrons inside middle cage. Applying an oriented external electric field (OEEF) of -20 × 10 au (-0.1018 V/Å) or a larger one can result in both left-to-right transfers of the two excess electrons, and then releasing the OEEF can form new kind of inter-cage electron-transfer isomers (III or IV). Each triplet I ~ IV with three redox sits may be new members of mixed-valent compounds, namely, Robin-Day Class II. For electrified I of (CF)&K , the following spin states are ground state: 1) triplet state in field ranges of -120 × 10 < F < -30 × 10 au and 30 × 10 < F < 111 × 10 au; 2) CS singlet state in range of F ≥ 111 × 10 and ≤ -120 × 10 au; 3) OS singlet state in ranges of -30 × 10 ≤ F ≤ -5 × 10 au and 5 × 10 ≤ F ≤ 30 × 10 au.

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Ammonia borane in an external electric field: structure, charge transfer, and chemical bonding

RSC Advances ◽

10.1039/c5ra10156e ◽

2015 ◽

Vol 5 (81) ◽

pp. 65991-65997 ◽

Cited By ~ 8

Author(s):

Xue Zhang ◽

Shi-Ling Sun ◽

Hong-Liang Xu ◽

Zhong-Min Su

Keyword(s):

Charge Transfer ◽

Electric Field ◽

External Electric Field ◽

Chemical Bonding ◽

Ammonia Borane ◽

Field Structure ◽

Donor Acceptor

It is well known that ammonia borane (BH3NH3) is one of the simplest donor–acceptor complexes.

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External Electric Field-Dependent Photoinduced Charge Transfer in a Donor–Acceptor System in Two-Photon Absorption

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.9b10086 ◽

2020 ◽

Vol 124 (4) ◽

pp. 2319-2332 ◽

Cited By ~ 19

Author(s):

Xijiao Mu ◽

Huan Zong ◽

Lilong Zhu ◽

Mengtao Sun

Keyword(s):

Charge Transfer ◽

Electric Field ◽

External Electric Field ◽

Photon Absorption ◽

Photoinduced Charge Transfer ◽

Two Photon Absorption ◽

Two Photon ◽

Field Dependent ◽

Donor Acceptor ◽

Photoinduced Charge

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Geometrical, electrical, and energetic parameters of hetero-disubstituted cumulenes and polyynes in the presence and absence of the external electric field

Structural Chemistry ◽

10.1007/s11224-021-01858-z ◽

2021 ◽

Author(s):

Nina Sadlej-Sosnowska ◽

Agnieszka Ocios-Bębenek ◽

Jan Cz. Dobrowolski ◽

Dariusz Boczar

Keyword(s):

Electric Field ◽

External Electric Field ◽

Molecular Electronics ◽

Energy Gap ◽

Carbon Chain ◽

Basis Set ◽

Polarizability Tensor ◽

Oh Groups ◽

Donor Acceptor ◽

Homo Lumo

AbstractCumulenes and polyynes have the potential to be applied as linear, sp-hybridized, one-dimensional all-carbon nanowires in molecular electronics and optoelectronics. The delocalization and conductivity descriptors of the two π-conjugated systems, heterodisubstituted with the NO2, CN, NH2, and OH groups, were studied using the B3LYP, B3LYP/D3, CAM-B3LYP, and ωB97XD DFT functionals, combined with the aug-cc-pVTZ basis set. Three independent types of molecular descriptors, based on geometry (the HOMA index), electrical properties (trace of the polarizability tensor), and energetic (the HOMO-LUMO energy gap) were shown to be mutually correlated and provided concordant indication that communication through the cumulene chain was considerably better than through the polyyne one. The communication can be tuned by using substituents of significantly different π-electron donor-acceptor properties as well as by the external electric field directed along the carbon chain.

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