Towards double-functionalized small diamondoids: selective electronic band-gap tuning

Adhikari, Bibek; Fyta, Maria

doi:10.1088/0957-4484/26/3/035701

Cited by 13 publications

(20 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For the ideal adamantane, the charge density for the HOMO is localized in between the carbon-hydrogen bonds and the charge density for the LUMO is delocalized and spread out over the molecule's surface. 47 The respective PDOS of the isolated NHC-ada molecules in the left panel of Fig. 3 are considerably altered by the presence of the carbene as compared to the ideal adamantane.…”

Section: Adsorption Energiesmentioning

confidence: 96%

“…3 are considerably altered by the presence of the carbene as compared to the ideal adamantane. 47 For both molecules, the s-orbitals contribute more to the electronic density of states in both the HOMO and the LUMO levels. A comparison of both carbene variations, NHC1 and NHC2, reveals that the s-and p-distributions in the PDOS are similarly broad.…”

Section: Adsorption Energiesmentioning

confidence: 98%

See 1 more Smart Citation

Carbene-mediated self-assembly of diamondoids on metal surfaces

2016

Self Cite

View full text Add to dashboard Cite

N-heterocyclic carbenes (NHC)s are emerging as an alternative class of molecules to thiol-based self-assembled monolayers (SAMs), making carbene-based SAMs much more stable under harsh environmental conditions. In this work, we have functionalized tiny diamondoids using NHCs in order to prepare highly stable carbene-mediated diamondoid SAMs on metal substrates. Using quantum-mechanical simulations and two different configurations for the carbene-functionalized diamondoids attached on gold, silver, and platinum surfaces we were able to study in detail these materials. Specifically, we focus on the binding characteristics, stability, and adsorption of the NHC-mediated diamondoid SAMs on the metal surfaces. A preferential binding to platinum surfaces was found, while a modulation of the work function in all cases was clear. The surface morphology of all NHC-based diamondoid SAMs was revealed through simulated STM images, which show characteristic features for each surface.

show abstract

Section: Adsorption Energiesmentioning

confidence: 96%

Section: Adsorption Energiesmentioning

confidence: 98%

Carbene-mediated self-assembly of diamondoids on metal surfaces

2016

Self Cite

View full text Add to dashboard Cite

show abstract

“…The electronic properties of diamondoids and small NDs have been investigated in numerous theoretical studies. 40,51,[59][60][61][62][63] Also, experimental results are available which give direct evidence on the electronic properties, i.e., the optical gaps of these systems. [39][40][41] For diamondoid optical gap calculations, Han and Bester demonstrated the necessity of including zero-point energy gap renormalization (ZPR) corrections to the calculated diamondoid electronic structures to account for coupling to nuclear vibrations.…”

Section: Electronic Structurementioning

confidence: 99%

Effects of oxidative adsorbates and cluster formation on the electronic structure of nanodiamonds

et al. 2022

View full text Add to dashboard Cite

Nanodiamonds (NDs) are modern high‐potential materials relevant for applications in biomedicine, photocatalysis, and various other fields. Their electronic surface properties, especially in the liquid phase, are key to their function in the applications, but we show that they are sensitively modified by their interactions with the environment. Two important interaction modes are those with oxidative aqueous adsorbates as well as ND self‐aggregation towards the formation of ND clusters. For planar diamond surfaces it is known that the electron density migrates from the diamond towards oxidative adsorbates, which is known as transfer doping. Here, we quantify this effect for highly curved NDs of varying sizes (35–147 C atoms) and surface terminations (H, OH, F), focusing on their interactions with the most abundant aqueous oxidative adsorbates (H3O+, O2, O3). We prove that the concept of transfer doping stays valid for the case of the high‐curvature NDs and can be tuned via the ND's specific properties. Secondly, we investigate the electronic structures of clusters of NDs which are known to form in particular in aqueous dispersions. Upon cluster formation, we find that the optical gaps of the structures are significantly reduced, which explains why different experimental values were obtained for the optical gap of the same structures, and the cluster's LUMO shapes resemble atom‐type orbitals, as in the case of isolated spherical NDs. Our findings have implications for ND applications as photocatalysts or electronic devices, where the specific electronic properties are key to the functionality of the ND material.

show abstract

“…Similarly, for the doped case the molecular conductance (Fermi level) was found to be3. 15 10 -G 3 0 for +0.9 and 3.33…”

Section: Typementioning

confidence: 99%

“…The electronic properties of diamondoids are influenced by the hydrogen terminations, a function with major consequences in the design of molecular-based diamondoids [13]. The influence of a single thiol functional group and other dopants on these properties has also been theoretically and experimentally determined [14,15]. Diamondoids show a monochromatic photoemission peak when forming monolayers [16].…”

Section: Introductionmentioning

confidence: 99%

Diamondoid-based molecular junctions: a computational study

Adhikari

Sivaraman²,

Fyta³

2016

Nanotechnology

Self Cite

View full text Add to dashboard Cite

In this work, we deal with the computational investigation of diamondoid-based molecular conductance junctions and their electronic transport properties. A small diamondoid is placed between the two gold electrodes of the nanogap and is covalently bonded to the gold electrodes through two different molecules, a thiol group and a N-heterocyclic carbene molecule. We have shown that the thiol linker is more efficient as it introduces additional electron paths for transport at lower energies. The influence of doping the diamondoid on the properties of the molecular junctions has been investigated. We find that using a nitrogen atom to dope the diamondoids leads to a considerable increase of the zero bias conductance. For the N-doped system we show an asymmetric feature of the I-V curve of the junctions resulting in rectification within a very small range of bias voltages. The rectifying nature is the result of the characteristic shift in the bias-dependent highest occupied molecular orbital state. In all cases, the efficiency of the device is manifested and is discussed in view of novel nanotechnological applications.

show abstract

Towards double-functionalized small diamondoids: selective electronic band-gap tuning

Cited by 13 publications

References 39 publications

Carbene-mediated self-assembly of diamondoids on metal surfaces

Carbene-mediated self-assembly of diamondoids on metal surfaces

Effects of oxidative adsorbates and cluster formation on the electronic structure of nanodiamonds

Diamondoid-based molecular junctions: a computational study

Contact Info

Product

Resources

About