Phenalenyl π-Dimer under the External Electric Field: Two-Electron/12-Center Bonding Breaking and Emergence of Electrostatic Interaction

Gao, Feng-Wei; Zhong, Rong‐Lin; Xu, Hong‐Liang; Su, Zhong‐Min

doi:10.1021/acs.jpcc.6b11732

Cited by 13 publications

(9 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[39][40][41][42] PLY p-dimer has been highlighted as a fascinating two-electron/ twelve center (2e/12c) bond originating from the overlap of two singly occupied molecular orbitals (SOMOs) of radical monomers. 43 Owing to the unique electronic and magnetic properties, PLY p-dimer and its derivatives have aroused increasing attention among scientists in many fields, [44][45][46][47][48][49][50] in which delocalized singlet biradical hydrocarbon (s-indaceno[1,2,3cd;5,6,7-c 0 d 0 ]diphenalene, IDPL) has been successfully isolated and characterized by Nakasuji et al 48 The one-dimensional (1D) chain of the multi-radical IDPL with a slipped stacking arrangement (see Scheme 1) exhibits an unusually short p-p distance (3.137 Å), which is less than a typical C-C van der Waals distance (3.400 Å). This report mainly described strong intra-and intermolecular interactions between two unpaired electrons and semiconductive behavior, which causes substantially close p-p contact.…”

Section: Introductionmentioning

confidence: 99%

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Gao

Muhammad

et al. 2018

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

An interesting biphenalenyl biradicaloid (IDPL) dimer consisting of both-middle superimposed phenalenyls and both-end nonsuperimposed phenalenyls has been synthesized, and has attracted intensive research interest due to its intra- and intermolecular interactions and semiconductive characteristics. It is significant that under regulation of the external electric field the directional charge transfer (CT) can produce attractive properties. In the present work, the structure and electronic properties of the IDPL dimer under an external electric field (along the horizontal Fx or the vertical Fz directions) are explored, and the following properties determined: (i) as the horizontal Fx increases, the intramolecular CT becomes larger, which induces the intermolecular CT of the IDPL dimer. (ii) In contrast, as the vertical Fz increases, the large intermolecular CT gives rise to the intramolecular CT of the IDPL dimer. (iii) More importantly, the external electric field effectively regulates and controls the first hyperpolarizability (βtot) of the IDPL dimer. Compared with the vertical Fz, the horizontal Fx induces a larger first hyperpolarizability (βtot = 5.48 × 105 a.u.). Furthermore, the application of a uniform external electric field (Fx,y,z) to the IDPL dimer was investigated to define the external electric field direction of the material application. The βtot values were increased with increasing of the uniform Fx,y,z. Our study provides an effective strategy for developing high-performance NLO materials by tuning the external electric field, and could be of significance for application in switch devices.

show abstract

Section: Introductionmentioning

confidence: 99%

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Gao

Muhammad

et al. 2018

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Considering the distribution of NBO charge, it was intriguing that with the NBO charge increasing, the Δ E value was decreased. This variation tendency caused by superalkali and superhalogen clusters was analogous to the effect of the external electric field, , although the effects were not great enough to change the bond property of the PLY dimer, and could not produce a great change of Δ E that could further determine the variation of β tot . However, when perfect nonlinear optical property of a material arises with a small Δ E value, the transparency of the material is always unsatisfactory.…”

Section: Resultsmentioning

confidence: 97%

Superatoms-Induced Effects of Phenalenyl π-Dimer on NICS and NLO Properties: Not Always Enhancement

Zhang

2017

J. Phys. Chem. C

Self Cite

View full text Add to dashboard Cite

The introduction of the Li3O and BeF3 can exhibit an interlayer charge-transfer transition character for pure phenalenyl (PLY) dimer. A considerable question emerged: Can we modulate the interlayer charge-transfer transition character with different superalkalis and superhalogens? In the present work, nine complexes were designed with three superalkalis (Li3O, Li3S, and Na3O) and three superhalogens (BeF3, BeCl3, and MgF3) introduced into the PLY dimers, respectively. Results showed that the geometric structure, interlayer charge transfer, and electron transition character of PLY dimer were alternated by the superalkalis and superhalogens, especially for superalkali, with the increasing atomic number for alkali metals, interlayer distance and interaction energy between PLY monomers increased, while first hyperpolarizability (βtot) decreased. The results of TD-DFT calculation indicated that the variation of βtot was mainly caused by the alteration of the difference of the dipole moments between the ground state and the crucial excited state Δμ. Otherwise, due to the introduction of superatoms, the distribution of HOMO and LUMO was changed greatly as compared to that of pure PLY dimer. In addition, aromaticity was also analyzed, and it was intriguing to find that introduction of superatoms caused asymmetric distribution of aromaticity along the central-carbon axis. All of the above consequences suggested that the introduction of superatoms was really an effective strategy to alter the structure and the nonlinear optical property of the system.

show abstract

“…There exists a radical-radical interaction in PLY dimer, which has been studied extensively. [80][81][82][83][84] The GKS-EDA (BS) result of PLY dimer at the U-ωB97X-D/6-311++G(d,p) level is shown in Figure 5(A). It is shown that the interaction is dominated by the correlation term.…”

Section: Two Body and Many Body Interactions In Iyqygg Segmentmentioning

confidence: 99%

XEDA, a fast and multipurpose energy decomposition analysis program

et al. 2021

View full text Add to dashboard Cite

A fast and multipurpose energy decomposition analysis (EDA) program, called XEDA, is introduced for quantitative analysis of intermolecular interactions. This program contains a series of variational EDA methods, including LMO-EDA, GKS-EDA and their extensions, to analyze non-covalent interactions and strong chemical bonds in various environments. XEDA is highly efficient with a similar computational scaling of single point energy calculations. Its efficiency and universality are validated by a series of test examples including van der Waals interactions, hydrogen bonds, radical-radical interactions and strong covalent bonds. | INTRODUCTIONEnergy decomposition analysis (EDA) methods have been widely used for the quantitative analysis of intermolecular interactions based on quantum mechanical calculations. [1][2][3][4][5][6][7][8][9][10][11][12] They divide total interaction energies of molecular systems into several physically meaningful components to explore the physical origin of intermolecular interactions. Over the past decades, lots of EDA methods have been proposed, which can be classified into three groups, perturbation EDA methods, 4-8 variational EDA methods, 9-34 and real-space EDA methods. [35][36][37] In 2009, a variational EDA method, named localized molecular orbitals-based EDA (LMO-EDA) was proposed by one of the present authors and coworker. 22 LMO-EDA can be used for exploring different weak and strong interactions by using Hartree-Fock (HF) and Kohn-Sham (KS) orbitals. To consider various interactions in complex systems, following LMO-EDA, 22 energy decomposition analysis with polarizable continuum model (EDA-PCM), 24 generalized Kohn-Sham energy decomposition analysis (GKS-EDA), 25 and their extensions, have been proposed in the last decade. EDA-PCM was developed for intermolecular interactions in the solvated environments. GKS-EDA is an improved version of LMO-EDA, overcoming some shortcomings when KS orbitals are applied.Recently, a new extension of GKS-EDA, named GKS-EDA(BS), 33 was presented for intermolecular interactions in open shell singlet (OSS) states, which are challenging for most of EDA methods due to the multi-reference character. These EDA methods are capable of handling various chemical problems, which were comprehensively reviewed in a recently published article. 11 Currently, the EDA methods mentioned above are implemented in various quantum chemical programs. For example, KM-EDA, 13 RVS-EDA, 17,18 and LMO-EDA 22 are included in the released version of GAMESS program; 38 ETS-NOCV-EDA 21 is implemented in ADF; 39 ALMO-EDA 20 is provided by Q-Chem. 40 Local-EDA 27 is available in ORCA. 41 SAPT 4-8 is involved in Q-Chem, 40 PSI4, 42 MOLPRO, 43 CamCASP, 44 and SAPT2020. 45 Our developed EDA methods were implemented in a home-made version of GAMESS. 38 Most recently, the GKS-EDA method has been implemented in Turbomole, 46 and used for the study of interactions in isoquinolinyl pyrazolate Pt(II) complexes. 47 Recently, all our developed EDA methods were reimplemented as a novel pro...

show abstract

Phenalenyl π-Dimer under the External Electric Field: Two-Electron/12-Center Bonding Breaking and Emergence of Electrostatic Interaction

Cited by 13 publications

References 56 publications

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Superatoms-Induced Effects of Phenalenyl π-Dimer on NICS and NLO Properties: Not Always Enhancement

XEDA, a fast and multipurpose energy decomposition analysis program

Contact Info

Product

Resources

About