Characterization of the Low-Energy Electronic Excited States of Benzoyl-Substituted Ruthenocenes

Although cyclo[18]carbon has been theoretically and experimentally investigated since long time ago, only very recently it was prepared and directly observed by means of STM/AFM in condensed phase (Kaiser et al., <i>Science</i>, <b>365</b>, 1299 (2019)). The unique ring structure and dual 18-center π delocalization feature bring a variety of unusual characteristics and properties to the cyclo[18]carbon, which are quite worth to be explored. In this work, we present an extremely comprehensive and detailed investigation on almost all aspects of the cyclo[18]carbon, including (1) Geometric characteristics (2) Bonding nature (3) Electron delocalization and aromaticity (4) Intermolecular interaction (5) Reactivity (6) Electronic excitation and UV/Vis spectrum (7) Molecular vibration and IR/Raman spectrum (8) Molecular dynamics (9) Response to external field (10) Electron ionization, affinity and accompanied process (11) Various molecular properties. We believe that our full characterization of the cyclo[18]carbon will greatly deepen researchers' understanding of this system, and thereby help them to utilize it in practice and design its various valuable derivatives.

Download Full-text

A Thorough Theoretical Exploration of Intriguing Characteristics of Cyclo[18]carbon: Geometry, Bonding Nature, Aromaticity, Weak Interaction, Reactivity, Excited States, Vibrations, Molecular Dynamics and Various Molecular Properties

10.26434/chemrxiv.11320130 ◽

2019 ◽

Cited By ~ 2

Author(s):

Tian Lu ◽

Qinxue Chen ◽

Zeyu Liu

Keyword(s):

Molecular Dynamics ◽

Excited States ◽

Electronic Excitation ◽

Ring Structure ◽

Molecular Properties ◽

Molecular Vibration ◽

Full Characterization ◽

Long Time ◽

Almost All

Although cyclo[18]carbon has been theoretically and experimentally investigated since long time ago, only very recently it was prepared and directly observed by means of STM/AFM in condensed phase (Kaiser et al., <i>Science</i>, <b>365</b>, 1299 (2019)). The unique ring structure and dual 18-center π delocalization feature bring a variety of unusual characteristics and properties to the cyclo[18]carbon, which are quite worth to be explored. In this work, we present an extremely comprehensive and detailed investigation on almost all aspects of the cyclo[18]carbon, including (1) Geometric characteristics (2) Bonding nature (3) Electron delocalization and aromaticity (4) Intermolecular interaction (5) Reactivity (6) Electronic excitation and UV/Vis spectrum (7) Molecular vibration and IR/Raman spectrum (8) Molecular dynamics (9) Response to external field (10) Electron ionization, affinity and accompanied process (11) Various molecular properties. We believe that our full characterization of the cyclo[18]carbon will greatly deepen researchers' understanding of this system, and thereby help them to utilize it in practice and design its various valuable derivatives.

Download Full-text

Excited State Tracking During the Relaxation of Coordination Compounds

10.26434/chemrxiv.7454702 ◽

2018 ◽

Author(s):

Juan Sanz García ◽

Martial Boggio-Pasqua ◽

Ilaria Ciofini ◽

Marco Campetella

Keyword(s):

Excited State ◽

Excited States ◽

Potential Energy Surfaces ◽

Photochemical Reactions ◽

Complex Nature ◽

Electronic Excited States ◽

Ruthenium Nitrosyl ◽

State Tracking ◽

Energy Surfaces ◽

Electronic Wavefunction

<div>The ability to locate minima on electronic excited states (ESs) potential energy surfaces (PESs) both in the case of bright and dark states is crucial for a full understanding of photochemical reactions. This task has become a standard practice for small- to medium-sized organic chromophores thanks to the constant developments in the field of computational photochemistry. However, this remains a very challenging effort when it comes to the optimization of ESs of transition metal complexes (TMCs), not only due to the presence of several electronic excited states close in energy, but also due to the complex nature of the excited states involved. In this article, we present a simple yet powerful method to follow an excited state of interest during a structural optimization in the case of TMC, based on the use of a compact hole-particle representation of the electronic transition, namely the natural transition orbitals (NTOs). State tracking using NTOs is unambiguously accomplished by computing the mono-electronic wavefunction overlap between consecutive steps of the optimization. Here, we demonstrate that this simple but robust procedure works not only in the case of the cytosine but also in the case of the ES optimization of a ruthenium-nitrosyl complex which is very problematic with standard approaches.</div>

Download Full-text

Electronic excited states of benzene in interaction with water clusters: influence of structure and size

Theoretical Chemistry Accounts ◽

10.1007/s00214-021-02764-7 ◽

2021 ◽

Vol 140 (6) ◽

Author(s):

Nadia Ben Amor ◽

Eric Michoulier ◽

Aude Simon

Keyword(s):

Excited States ◽

Water Clusters ◽

Electronic Excited States

Download Full-text

Influence of TOPO and TOPO-CdSe/ZnS Quantum Dots on Luminescence Photodynamics of InP/InAsP/InPHeterostructure Nanowires

Nanomaterials ◽

10.3390/nano11030640 ◽

2021 ◽

Vol 11 (3) ◽

pp. 640

Author(s):

Artem I. Khrebtov ◽

Vladimir V. Danilov ◽

Anastasia S. Kulagina ◽

Rodion R. Reznik ◽

Ivan D. Skurlov ◽

...

Keyword(s):

Quantum Dots ◽

Excited States ◽

Molecular Beam ◽

Surface Passivation ◽

Low Energy ◽

Trioctylphosphine Oxide ◽

Reverse Transfer ◽

Semiconductor Heterostructure ◽

Ligand Type

The passivation influence by ligands coverage with trioctylphosphine oxide (TOPO) and TOPO including colloidal CdSe/ZnS quantum dots (QDs) on optical properties of the semiconductor heterostructure, namely an array of InP nanowires (NWs) with InAsP nanoinsertion grown by Au-assisted molecular beam epitaxy on Si (111) substrates, was investigated. A significant dependence of the photoluminescence (PL) dynamics of the InAsP insertions on the ligand type was shown, which was associated with the changes in the excitation translation channels in the heterostructure. This change was caused by a different interaction of the ligand shells with the surface of InP NWs, which led to the formation of different interfacial low-energy states at the NW-ligand boundary, such as surface-localized antibonding orbitals and hybridized states that were energetically close to the radiating state and participate in the transfer of excitation. It was shown that the quenching of excited states associated with the capture of excitation to interfacial low-energy traps was compensated by the increasing role of the “reverse transfer” mechanism. As a result, the effectiveness of TOPO-CdSe/ZnS QDs as a novel surface passivation coating was demonstrated.

Download Full-text