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Title: Transferrable property relationships between magnetic exchange coupling and molecular conductance
Calculated conductance through Au n –S–Bridge–S–Au n (Bridge = organic σ/π-system) constructs are compared to experimentally-determined magnetic exchange coupling parameters in a series of Tp Cum,Me ZnSQ–Bridge–NN complexes, where Tp Cum,Me = hydro-tris(3-cumenyl-1-methylpyrazolyl)borate ancillary ligand, Zn = diamagnetic zinc( ii ), SQ = semiquinone ( S = 1/2), and NN = nitronylnitroxide radical ( S = 1/2). We find that there is a nonlinear functional relationship between the biradical magnetic exchange coupling, J D→A , and the computed conductance, g mb . Although different bridge types (monomer vs. dimer) do not lie on the same J D→A vs. g mb , curve, there is a scale invariance between the monomeric and dimeric bridges which shows that the two data sets are related by a proportionate scaling of J D→A . For exchange and conductance mediated by a given bridge fragment, we find that the ratio of distance dependent decay constants for conductance ( β g ) and magnetic exchange coupling ( β J ) does not equal unity, indicating that inherent differences in the tunneling energy gaps, Δ ε , and the bridge–bridge electronic coupling, H BB , are not directly transferrable properties as they relate to exchange and conductance. more » The results of these observations are described in valence bond terms, with resonance structure contributions to the ground state bridge wavefunction being different for SQ–Bridge–NN and Au n –S–Bridge–S–Au n systems. « less
Authors:
; ; ; ; ;
Award ID(s):
1764181
Publication Date:
NSF-PAR ID:
10269516
Journal Name:
Chemical Science
Volume:
11
Issue:
42
Page Range or eLocation-ID:
11425 to 11434
ISSN:
2041-6520
Sponsoring Org:
National Science Foundation
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Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018).« less