Vertical <i>vs.</i> adiabatic ionization energies in solution and gas-phase: probing ionization-induced reorganization in conformationally-mobile bichromophoric actuators using photoelectron spectroscopy, electrochemistry and theory

Ivanov, Maxim V.; Wang, Denan; Zhang, Depeng; Rathore, Rajendra; Reid, Scott A.

doi:10.1039/c8cp02936a

Cited by 11 publications

(15 citation statements)

References 43 publications

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“…In contrast, the push-back effect is presumably responsible for the small work function change caused by the adsorption of DBP on h-BN/Ni(111). Furthermore, we determined the adiabatic and vertical ionization energy as distance of the onset and the peak maximum of the HOMO-derived feature to the vacuum level, respectively [ 38 ]. Therefore, we used Gaussian fits of the UP spectra in Fig.…”

Section: Resultsmentioning

confidence: 99%

Hybridization vs decoupling: influence of an h-BN interlayer on the physical properties of a lander-type molecule on Ni(111)

Schaal¹,

Aihara²,

Gruenewald³

et al. 2020

Beilstein J. Nanotechnol.

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2D materials such as hexagonal boron nitride (h-BN) are widely used to decouple organic molecules from metal substrates. Nevertheless, there are also indications in the literature for a significant hybridization, which results in a perturbation of the intrinsic molecular properties. In this work we study the electronic and optical properties as well as the lateral structure of tetraphenyldibenzoperiflanthene (DBP) on Ni(111) with and without an atomically thin h-BN interlayer to investigate its possible decoupling effect. To this end, we use in situ differential reflectance spectroscopy as an established method to distinguish between hybridized and decoupled molecules. By inserting an h-BN interlayer we fabricate a buried interface and show that the DBP molecules are well decoupled from the Ni(111) surface. Furthermore, a highly ordered DBP monolayer is obtained on h-BN/Ni(111) by depositing the molecules at a substrate temperature of 170 °C. The structural results are obtained by quantitative low-energy electron diffraction and low-temperature scanning tunneling microscopy. Finally, the investigation of the valence band structure by ultraviolet photoelectron spectroscopy shows that the low work function of h-BN/Ni(111) further decreases after the DBP deposition. For this reason, the h-BN-passivated Ni(111) surface may serve as potential n-type contact for future molecular electronic devices.

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Section: Resultsmentioning

confidence: 99%

Hybridization vs decoupling: influence of an h-BN interlayer on the physical properties of a lander-type molecule on Ni(111)

Schaal¹,

Aihara²,

Gruenewald³

et al. 2020

Beilstein J. Nanotechnol.

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“…The obtained values of solvent phase adiabatic ionisation energies (AIE=Δ G (RC relaxed ) – Δ G( IB or IBA relaxed )) (recommended for correlating with oxidation potentials by Ivanov et al [15] 5.…”

Section: Resultsmentioning

confidence: 99%

Anodic Oxidation of Iodobenzene and Iodobenzoic Acids in Acetic Acid Environment – Electrochemical Investigation and Density Functional Theory Study

et al. 2021

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Kinetic and mechanistic aspects of an anodic oxidation of iodobenzene and its selected derivatives leading to the corresponding iodosyl compounds, were investigated in anhydrous acidic acetic acid environment using boron‐doped diamond electrode. The first electron removal leading to the formation of radical cation was identified as the rate determining step of the process. Oxidation potential values of the investigated compounds were rationalised by their solution phase ionisation energies (in conformation of the radical cations as products of the first electron removal), calculated by advanced DFT methods. Unexpectedly low oxidation potential of 2‐iodobenzoic acid and its functional derivatives compared to iodobenzene, 3‐iodo and 4‐iodobenzoic acids was explained by decreased electron density at iodine atom leading to planar 2‐iodobenzoic acid radical cation. This is connected with reordering of its frontier molecular orbitals compared to non‐planar neutral molecule.

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“…Although the intrinsic BDE INT may be similar for different metals, the energy needed to prepare the metal for this bonding may vary substantially, resulting in corresponding variations in BDEs to ground-state metal and halogen atoms. This distinction between hypothetical intrinsic dissociation and actual dissociation is analogous to that between vertical and adiabatic ionization . Treating the dissociation of LnX as occurring to atoms Ln and X with electronic configurations similar to those in the molecule presupposes molecular orbitals derived from atomic orbitals, such as by a linear combination of atomic orbitals (LCAO), a well-founded notion described early on by Pauling and Mulliken .…”

Section: Introductionmentioning

confidence: 99%

“…This distinction between hypothetical intrinsic dissociation and actual dissociation is analogous to that between vertical and adiabatic ionization. 33 Treating the dissociation of LnX as occurring to atoms Ln and X with electronic configurations similar to those in the molecule 34 presupposes molecular orbitals derived from atomic orbitals, such as by a linear combination of atomic orbitals (LCAO), 35 a well-founded notion described early on by Pauling 36 and Mulliken. 37 Although simplistic concepts such as LCAO can be constraining, 38 their demonstrated validity presents opportunities to rationalize the molecular character based on atomic properties.…”

Section: ■ Introductionmentioning

confidence: 99%

Bond Dissociation Energies Reveal the Participation of d Electrons in f-Element Halide Bonding

Gibson

2022

J. Phys. Chem. A

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Bond dissociation energies (BDEs) reported in the literature for lanthanide monofluorides and lanthanide monochlorides LnX, where X = F or Cl, exhibit substantial irregular variations across the Ln series. It is demonstrated here that correlations of these variations with reported experimentally based atomic energies to prepare the Ln constituent for bonding reveal the nature of the bonding. Whereas some molecular characteristics are well understood in the context of highly ionic bonding, with LnX considered to be (Ln + )(X − ), some significant variations in BDEs are not well rationalized simply by ionization to convert Ln to Ln + for bonding. Focusing here on lanthanide monofluorides LnF, a consideration of alternative Ln preparation schemes shows that a particularly good rationalization of BDEs is obtained by invoking the participation of a lanthanide 5d electron in bonding. This 5d participation could be in ionic (Ln + )(F − ) via π-donation from F − 2p to empty Ln + 5d orbitals or in covalent πbonded Ln:F via polarization from Ln 5d to F 2p, with these ionic and polar covalent perspectives ultimately being equivalent. The inference of lanthanide 5d involvement suggests that the valence 4f and 6s electrons do not effectively participate in some key aspects of the bonding, presumably due to poor spatial overlap with F 2p orbitals. An extension to actinide monofluorides, AnF, assumes analogous ionic or polar covalent bonding involving a valence 6d electron and results in predictions for BDEs that include a general decrease from left to right across the series, except for a distinctive local minimum at AmF. Determining the BDE for AmF would serve to evaluate the predictions and the underlying assumption of 6d bonding. The BDE assessments/predictions for neutral monofluorides, LnF and AnF, are also applied to cationic LnF + and AnF + , and it is noted that the approach can be directly extended to f-element monochlorides, monobromides, and monoiodides.

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Vertical vs. adiabatic ionization energies in solution and gas-phase: probing ionization-induced reorganization in conformationally-mobile bichromophoric actuators using photoelectron spectroscopy, electrochemistry and theory

Abstract: Ionization-induced structural and conformational reorganization is probed in various π-stacked dimers and covalently linked bichromophores.

Cited by 11 publications

References 43 publications

Hybridization vs decoupling: influence of an h-BN interlayer on the physical properties of a lander-type molecule on Ni(111)

Hybridization vs decoupling: influence of an h-BN interlayer on the physical properties of a lander-type molecule on Ni(111)

Anodic Oxidation of Iodobenzene and Iodobenzoic Acids in Acetic Acid Environment – Electrochemical Investigation and Density Functional Theory Study

Bond Dissociation Energies Reveal the Participation of d Electrons in f-Element Halide Bonding

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