Universal latent electron-donor anions with negative gas-phase electron detachment energies (Conference Presentation)

2019 ◽  
Author(s):  
Peter Ho
Keyword(s):  
Gas Phase ◽  
Electron Donor ◽  
Electron Detachment

Nitric Oxide as an Electron Donor, an Atom Donor, an Atom Acceptor, and a Ligand in Reactions with Atomic Transition-Metal and Main-Group Cations in the Gas Phase

2005 ◽  
Vol 109 (49) ◽  
pp. 11224-11235 ◽  
Author(s):  
Voislav Blagojevic ◽  
Eric Flaim ◽  
Michael J. Y. Jarvis ◽  
Gregory K. Koyanagi ◽  
Diethard K. Bohme
Keyword(s):  
Nitric Oxide ◽  
Transition Metal ◽  
Gas Phase ◽  
Electron Donor ◽  
Main Group ◽  
Atomic Transition

On the stabilization of the carbonate dianion by sulfur dioxide

2010 ◽  
Vol 88 (11) ◽  
pp. 1125-1135 ◽  
Author(s):  
Friedrich Grein ◽  
Justin K. Chan ◽  
Idlir Liko
Keyword(s):  
Sulfur Dioxide ◽  
Oxygen Atom ◽  
Gas Phase ◽  
Single Point ◽  
Basis Set ◽  
Water Molecules ◽  
Electron Detachment ◽  
Optimized Geometries

The stabilization in the gas phase of the carbonate dianion [Formula: see text] by SO2 molecules is being investigated. The geometries of various isomers of [Formula: see text] (SO2)n and [Formula: see text] (SO2)n, for n = 1–4, have been optimized by the B3PW91/6−311+G(3df) method. Single-point CCSD and CCSD(T) energies at the DFT-optimized geometries were obtained for n = 1–3, using the 6−311+G(d) basis set. For n = 1 and 2, the monoanionic clusters are adiabatically more stable than the dianionic ones. However, starting at n = 3, they become less stable. The CCSD adiabatic electron detachment energy of the dianionic cluster switches from −0.39 eV for n = 2 to +0.20 eV for n = 3. The vertical electron detachment energy turns positive at n = 2, with a CCSD value of 1.35 eV. Several of the less stable dianionic, and most of the monoionic clusters, are characterized by the transfer of an oxygen atom from CO3 to SO2, forming [Formula: see text] or [Formula: see text] units, owing to [Formula: see text] + CO2 being more stable than [Formula: see text] + SO2. For the stabilization of the sulfate dianion by stepwise hydration, studied both experimentally and theoretically by other groups, a minimum of three water molecules was required.

scholarly journals Sterische Effekte auf die Hydrierstabilität von 1, 1′-Dialkyl-4,4′-bipyridiniumsalzen (Viologenen) in wasserphotolytischen Systemen / Steric Effects on the Hydrogen Stability of 1,1′-Dialkyl-4,4′-bipyridinium Salts (Viologens) in Water Photolytic Systems

1991 ◽  
Vol 46 (11) ◽  
pp. 1544-1548 ◽  
Author(s):  
Rupert Bauer ◽  
Christian Königstein
Keyword(s):  
Gas Phase ◽  
Electron Donor ◽  
Chemical Stability ◽  
Platinum Catalyst ◽  
Steric Effects ◽  
Quantum Yields ◽  
Practical Applications

The chemical stability of 1,1′-dialkyl-4,4′-bipyridinium compounds (viologens) as electron relay agents in hydrogen producing water photolytic systems is of great importance for practical applications. Three new 1,1′-dialkyl-4,4′-bipyridinium compounds (1 = 1,1′-dimethyl-2-phenyl-6-(p-tolyl)-4,4′-bipyridiniumdiperchlorate, 2 = 1,1′-dimethyl-2-phenyl-4,4′-bipyridiniumdiperchlorate, 3 = 6-phenyl-1,1′,2-trimethyl-4,4′-bipyridiniumdiperchlorate) have been investigated with respect to their stability and turnover numbers in a classical water photolytic system. H2 was detected during irradiation of solutions using Ru(bipy)3Cl2 as sensitizer, 1-3 as electron relay, EDTA as sacrificial electron donor, and a colloidal catalyst (platinum or palladium) with light λ > 400 nm. Quantum yields (platinum catalyst, light: 400-500 nm) were 18% 1 and 3, 16% 2, compared with methylviologen: 16%. The loss of 1,1′-dialkyl-4,4′-bipyridinium compounds due to hydrogenation was monitored by HPLC. Turnover Numbers (only hydrogen in gas phase was taken into account) were found to be 82 1, 64 2, 57 3 as compared with 39 for methylviologen. Using palladium or palladium supported on BaSO4 instead of platinum as catalysts did not increase the turnover numbers.

scholarly journals Electron Donor and Acceptor Influence on the Nonlinear Optical Response of Diacetylene-Functionalized Organic Materials (DFOMs): Density Functional Theory Calculations

Molecules ◽  
2019 ◽  
Vol 24 (11) ◽  
pp. 2096 ◽  
Author(s):  
Muhammad Khalid ◽  
Riaz Hussain ◽  
Ajaz Hussain ◽  
Bakhat Ali ◽  
Farrukh Jaleel ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Gas Phase ◽  
Electron Donor ◽  
Density Functional ◽  
Nbo Analysis ◽  
Basis Set ◽  
First Hyperpolarizability ◽  
Functional Theory ◽  
Parent Molecule ◽  
Donor And Acceptor

Herein, we report the quantum chemical results based on density functional theory for the polarizability (α) and first hyperpolarizability (β) values of diacetylene-functionalized organic molecules (DFOM) containing an electron acceptor (A) unit in the form of nitro group and electron donor (D) unit in the form of amino group. Six DFOM 1–6 have been designed by structural tailoring of the synthesized chromophore 4,4′-(buta-1,3-diyne-1,4-diyl) dianiline (R) and the influence of the D and A moieties on α and β was explored. Ground state geometries, HOMO-LUMO energies, and natural bond orbital (NBO) analysis of all DFOM (R and 1–6) were explored through B3LYP level of DFT and 6-31G(d,p) basis set. The polarizability (α), first hyperpolarizability (β) values were computed using B3LYP (gas phase), CAM-B3LYP (gas phase), CAM-B3LYP (solvent DMSO) methods and 6-31G(d,p) basis set combination. UV-Visible analysis was performed at CAM-B3LYP/6-31G(d,p) level of theory. Results illustrated that much reduced energy gap in the range of 2.212–2.809 eV was observed in designed DFOM 1–6 as compared to parent molecule R (4.405 eV). Designed DFOM (except for 2 and 4) were found red shifted compared to parent molecule R. An absorption at longer wavelength was observed for 6 with 371.46 nm. NBO analysis confirmed the involvement of extended conjugation and as well as charge transfer character towards the promising NLO response and red shift of molecules under study. Overall, compound 6 displayed large <α> and βtot, computed to be 333.40 (a.u.) (B3LYP gas), 302.38 (a.u.) (CAM-B3LYP gas), 380.46 (a.u.) (CAM-B3LYP solvent) and 24708.79 (a.u.), 11841.93 (a.u.), 25053.32 (a.u.) measured from B3LYP (gas), CAM-B3LYP (gas) and CAM-B3LYP (DMSO) methods respectively. This investigation provides a theoretical framework for conversion of centrosymmetric molecules into non-centrosymmetric architectures to discover NLO candidates for modern hi-tech applications.

C??C Backbone Fragmentation Dominates in Electron Detachment Dissociation of Gas-Phase Polypeptide Polyanions

2005 ◽  
Vol 11 (6) ◽  
pp. 1803-1812 ◽  
Author(s):  
Frank Kjeldsen ◽  
Oleg A. Silivra ◽  
Igor A. Ivonin ◽  
Kim F. Haselmann ◽  
Mikhail Gorshkov ◽  
...  
Keyword(s):  
Gas Phase ◽  
Electron Detachment Dissociation ◽  
Electron Detachment
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