scholarly journals Diabatic states, nonadiabatic coupling, and the counterpoise procedure for weakly interacting open-shell molecules

2018 ◽  
Vol 148 (9) ◽  
pp. 094105 ◽  
Author(s):  
Tijs Karman ◽  
Matthieu Besemer ◽  
Ad van der Avoird ◽  
Gerrit C. Groenenboom
Keyword(s):  
Open Shell ◽  
Nonadiabatic Coupling ◽  
Diabatic States ◽  
Weakly Interacting

Search for weakly interacting massive dark matter particles: state of the art and prospects

2020 ◽  
Author(s):  
Andrei B. Aleksandrov ◽  
Aigerim B. Dashkina ◽  
Nina S. Konovalova ◽  
Natal'ya M. Okat'eva ◽  
Natal'ya G. Polukhina ◽  
...  
Keyword(s):  
Dark Matter ◽  
State Of The Art ◽  
Weakly Interacting

The Interplay of Open-Shell Spin-Coupling and Jahn-Teller Distortion in Benzene Radical Cation Probed by X-ray Spectroscopy

2020 ◽  
Author(s):  
Marta L. Vidal ◽  
Michael Epshtein ◽  
Valeriu Scutelnic ◽  
Zheyue Yang ◽  
Tian Xue ◽  
...  
Keyword(s):  
High Harmonic ◽  
Open Shell ◽  
Spin Coupling ◽  
High Symmetry ◽  
Teller Distortion ◽  
Spectral Window ◽  
X Ray ◽  
Jahn Teller ◽  
X Ray Absorption ◽  
Jahn Teller Distortion

We report a theoretical investigation and elucidation of the x-ray absorption spectra of neutral benzene and of the benzene cation. The generation of the cation by multiphoton ultraviolet (UV) ionization as well as the measurement of<br>the carbon K-edge spectra of both species using a table-top high-harmonic generation (HHG) source are described in the companion experimental paper [M. Epshtein et al., J. Phys.<br>Chem. A., submitted. Available on ChemRxiv]. We show that the 1sC -> pi transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence<br>of the unpaired (spectator) electron in the pi-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC ->pi* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation.<br>The prominent split structure of the 1sC -> pi* band of the cation is attributed to the interplay between the coupling of the core -> pi* excitation with the unpaired electron<br>in the pi-subshell and the Jahn-Teller distortion. The calculations attribute most of<br>the splitting (~1-1.2 eV) to the spin coupling, which is visible already at the Franck-Condon structure, and estimate the additional splitting due to structural relaxation to<br>be around ~0.1-0.2 eV. These results suggest that x-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn-Teller<br>effect in benzene cation.<br>

Room Temperature Alkali Metal Reduction of Carbon Dioxide

2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Bond Cleavage ◽  
Open Shell ◽  
Metal Reduction ◽  
One Pot ◽  
Earth Abundant ◽  
Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>

Form Factor of an Open-Shell Atom

2000 ◽  
Vol 89 (1) ◽  
pp. 4
Author(s):  
A. N. Khoperskiı̆
Keyword(s):  
Form Factor ◽  
Open Shell

Open shell CNDO treatments on small inorganic radicals

1973 ◽  
Vol 38 (10) ◽  
pp. 3067-3073 ◽  
Author(s):  
P. Čársky ◽  
M. Macháček ◽  
R. Zahradník
Keyword(s):  
Open Shell

Elektronenspektren der open-shell-Systeme

1974 ◽  
Vol 39 (3) ◽  
pp. 812-820 ◽  
Author(s):  
R. Stösser ◽  
P. Janietz ◽  
J. Sauer ◽  
C. Jung
Keyword(s):  
Open Shell
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