scholarly journals Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV

2017 ◽  
Vol 8 ◽  
pp. 2208-2218 ◽  
Author(s):  
Mónica Mendes ◽  
Khrystyna Regeta ◽  
Filipe Ferreira da Silva ◽  
Nykola C Jones ◽  
Søren Vrønning Hoffmann ◽  
...  
Keyword(s):  
Electron Scattering ◽  
Cross Sections ◽  
Lower Energy ◽  
Density Functional ◽  
Vacuum Ultraviolet ◽  
Energy Bands ◽  
Ligand Charge Transfer ◽  
Comprehensive Knowledge ◽  
Relativistic Time ◽  
Electronically Excited

High-resolution vacuum ultraviolet photoabsorption measurements in the wavelength range of 115–320 nm (10.8–3.9 eV) have been performed together with comprehensive relativistic time-dependent density functional calculations (TDDFT) on the low-lying excited sates of tungsten hexacarbonyl, W(CO)6. The higher resolution obtained reveals previously unresolved spectral features of W(CO)6. The spectrum shows two higher-energy bands (in the energy ranges of 7.22–8.12 eV and 8.15–9.05 eV), one of them with clear vibrational structure, and a few lower-energy shoulders in addition to a couple of lower-energy metal-to-ligand charge-transfer (MLCT) bands reported in the literature before. Absolute photoabsorption cross sections are reported and, where possible, compared to previously published results. On the basis of this combined experimental/theoretical study the absorption spectrum of the complex has been totally re-assigned between 3.9 and 10.8 eV under the light of spin–orbit coupling (SOC) effects. The present comprehensive knowledge of the nature of the electronically excited states may be of relevance to estimate neutral dissociation cross sections of W(CO)6, a precursor molecule in focused electron beam induced deposition (FEBID) processes, from electron scattering measurements.

scholarly journals Astrochemical relevance of VUV ionization of large PAH cations

2020 ◽  
Vol 641 ◽  
pp. A98 ◽  
Author(s):  
G. Wenzel ◽  
C. Joblin ◽  
A. Giuliani ◽  
S. Rodriguez Castillo ◽  
G. Mulas ◽  
...  
Keyword(s):  
Cross Sections ◽  
Density Functional ◽  
Interstellar Dust ◽  
Vacuum Ultraviolet ◽  
Branching Ratio ◽  
Molecular Size ◽  
Photoelectric Effect ◽  
Interstellar Gas ◽  
Ionization Cross Sections ◽  
The Impact

Context. As part of interstellar dust, polycyclic aromatic hydrocarbons (PAHs) are processed by an interaction with vacuum ultraviolet (VUV) photons emitted by hot stars. This interaction leads to the emission of not only the well-known aromatic infrared bands, but also electrons, which can significantly contribute to the heating of the interstellar gas. Aims. Our aim is to investigate the impact of molecular size on the photoionization properties of cationic PAHs. Methods. Trapped PAH cations of sizes between 30 and 48 carbon atoms were submitted to VUV photons in the range of 9–20 eV from the DESIRS beamline at the synchrotron SOLEIL. All resulting photoproducts including dications and fragment cations were mass-analyzed and recorded as a function of photon energy. Results. Photoionization is found to be predominant over dissociation at all energies, which differs from the conclusions of an earlier study on smaller PAHs. The photoionization branching ratio reaches 0.98 at 20 eV for the largest studied PAH. The photoionization threshold is observed to be between 9.1 and 10.2 eV, in agreement with the evolution of the ionization potential with size. Ionization cross sections were indirectly obtained and photoionization yields extracted from their ratio with theoretical photoabsorption cross sections, which were calculated using time-dependent density functional theory. An analytical function was derived to calculate this yield for a given molecular size. Conclusions. Large PAH cations could be efficiently ionized in H I regions and contribute to the heating of the gas by the photoelectric effect. Also, at the border of or in H II regions, PAHs could be exposed to photons of energy higher than 13.6 eV. Our work provides recipes to be used in astronomical models to quantify these points.

A density functional theory and spectroscopic study of intramolecular quenching of metal-to-ligand charge-transfer excited states in some mono-bipyridine ruthenium(II) complexes

2014 ◽  
Vol 92 (10) ◽  
pp. 996-1009 ◽  
Author(s):  
Shivnath Mazumder ◽  
Ryan A. Thomas ◽  
Richard L. Lord ◽  
H. Bernhard Schlegel ◽  
John F. Endicott
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Charge Transfer ◽  
Excited States ◽  
Lower Energy ◽  
Density Functional ◽  
Dimethyl Sulfide ◽  
Intramolecular Electron Transfer ◽  
Functional Theory ◽  
Ligand Charge Transfer

The complexes [Ru(NCCH3)4bpy]2+ and [Ru([14]aneS4)bpy]2+ ([14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane, bpy = 2,2′-bipyridine) have similar absorption and emission spectra but the 77 K metal-to-ligand charge-transfer (MLCT) excited state emission lifetime of the latter is less than 0.3% that of the former. Density functional theory modeling of the lowest energy triplet excited states indicates that triplet metal centered (3MC) excited states are about 3500 cm−1 lower in energy than their 3MLCT excited states in both complexes. The differences in excited state lifetimes arise from a much larger coordination sphere distortion for [Ru(NCCH3)4bpy]2+ and the associated larger reorganizational barrier for intramolecular electron transfer. The smaller ruthenium ligand distortions of the [Ru([14]aneS4)bpy]2+ complex are apparently a consequence of stereochemical constraints imposed by the macrocyclic [14]aneS4 ligand, and the 3MC excited state calculated for the unconstrained [Ru(S(CH3)2)4bpy]2+ complex (S(CH3)2 = dimethyl sulfide) is distorted in a manner similar to that of [Ru(NCCH3)4bpy]2+. Despite the lower energy calculated for its 3MC than 3MLCT excited state, [Ru(NCCH3)4bpy]2+ emits strongly in 77 K glasses with an emission quantum yield of 0.47. The emission is biphasic with about a 1 μs lifetime for its dominant (86%) emission component. The 405 nm excitation used in these studies results in a significant amount of photodecomposition in the 77 K glasses. This is a temperature-dependent biphotonic process that most likely involves the bipyridine-radical anionic moiety of the 3MLCT excited state. A smaller than expected value found for the radiative rate constant is consistent with a lower energy 3MC than 3MLCT state.

scholarly journals Excited States of Bromopyrimidines Probed by VUV Photoabsorption Spectroscopy and Theoretical Calculations

2021 ◽  
Vol 22 (12) ◽  
pp. 6460
Author(s):  
Mónica Mendes ◽  
Fábris Kossoski ◽  
Ana I. Lozano ◽  
João Pereira-da-Silva ◽  
Rodrigo Rodrigues ◽  
...  
Keyword(s):  
Absorption Band ◽  
Cross Sections ◽  
Density Functional ◽  
Vacuum Ultraviolet ◽  
Theoretical Calculations ◽  
Broad Band ◽  
Rydberg States ◽  
Detailed Comparison ◽  
Absorption Data ◽  
Franck Condon

We report absolute photoabsorption cross sections for gas-phase 2- and 5-bromopyrimidine in the 3.7–10.8 eV energy range, in a joint theoretical and experimental study. The measurements were carried out using high-resolution vacuum ultraviolet synchrotron radiation, with quantum chemical calculations performed through the nuclear ensemble approach in combination with time-dependent density functional theory, along with additional Franck–Condon Herzberg–Teller calculations for the first absorption band (3.7–4.6 eV). The cross sections of both bromopyrimidines are very similar below 7.3 eV, deviating more substantially from each other at higher energies. In the 7.3–9.0 eV range where the maximum cross-section is found, a single and broad band is observed for 5-bromopyrimidine, while more discernible features appear in the case of 2-bromopyrimidine. Several π* ← π transitions account for the most intense bands, while weaker ones are assigned to transitions involving the nitrogen and bromine lone pairs, the antibonding σ*Br orbital, and the lower-lying Rydberg states. A detailed comparison with the available photo-absorption data of bromobenzene is also reported. We have found significant differences regarding the main absorption band, which is more peaked in bromobenzene, becoming broader and shifting to higher energies in both bromopyrimidines. In addition, there is a significant suppression of vibrational structures and of Rydberg states in the pair of isomers, most noticeably for 2-bromopyrimidine.

Electron Scattering in Solids

1990 ◽  
Vol 48 (2) ◽  
pp. 4-5
Author(s):  
Ryuichi Shimizu ◽  
Ze-Jun Ding
Keyword(s):  
Monte Carlo Simulation ◽  
Monte Carlo ◽  
Angular Distribution ◽  
Elastic Scattering ◽  
Electron Scattering ◽  
Cross Sections ◽  
Expansion Method ◽  
Electron Excitation ◽  
Partial Wave Expansion ◽  
Backscattered Electrons

Monte Carlo simulation has been becoming most powerful tool to describe the electron scattering in solids, leading to more comprehensive understanding of the complicated mechanism of generation of various types of signals for microbeam analysis.The present paper proposes a practical model for the Monte Carlo simulation of scattering processes of a penetrating electron and the generation of the slow secondaries in solids. The model is based on the combined use of Gryzinski’s inner-shell electron excitation function and the dielectric function for taking into account the valence electron contribution in inelastic scattering processes, while the cross-sections derived by partial wave expansion method are used for describing elastic scattering processes. An improvement of the use of this elastic scattering cross-section can be seen in the success to describe the anisotropy of angular distribution of elastically backscattered electrons from Au in low energy region, shown in Fig.l. Fig.l(a) shows the elastic cross-sections of 600 eV electron for single Au-atom, clearly indicating that the angular distribution is no more smooth as expected from Rutherford scattering formula, but has the socalled lobes appearing at the large scattering angle.

scholarly journals Relativistic B-Spline R-Matrix Calculations for Electron Collisions with Ytterbium

Atoms ◽  
2021 ◽  
Vol 9 (3) ◽  
pp. 47
Author(s):  
Kathryn R. Hamilton ◽  
Klaus Bartschat ◽  
Oleg Zatsarinny
Keyword(s):  
Experimental Data ◽  
Electron Scattering ◽  
Cross Sections ◽  
Matrix Method ◽  
Model Potential ◽  
Electron Collisions ◽  
R Matrix ◽  
B Spline ◽  
Potential Approach

We have applied the full-relativistic Dirac B-Spline R-matrix method to obtain cross sections for electron scattering from ytterbium atoms. The results are compared with those obtained from a semi-relativistic (Breit-Pauli) model-potential approach and the few available experimental data.

Total electron scattering cross-sections for carbon monoxide at low electron energies

Pramana ◽  
1998 ◽  
Vol 51 (3-4) ◽  
pp. 453-461 ◽  
Author(s):  
P. Rawat ◽  
K. P. Subramanian ◽  
Vijay Kumar
Keyword(s):  
Carbon Monoxide ◽  
Electron Scattering ◽  
Cross Sections ◽  
Total Electron ◽  
Scattering Cross ◽  
Scattering Cross Sections
Sign in / Sign up

Export Citation Format

Share Document