Two phosphaalkene radical cations with inverse spin density distributions

2015 ◽  
Vol 44 (34) ◽  
pp. 15099-15102 ◽  
Author(s):  
Xiaobo Pan ◽  
Xingyong Wang ◽  
Zaichao Zhang ◽  
Xinping Wang
Keyword(s):  
Spin Density ◽  
Radical Cations ◽  
Density Distributions ◽  
Weakly Coordinating ◽  
Weakly Coordinating Anion

Two phosphaalkene radical cations have been made by using a weakly coordinating anion, and they exhibit inverse spin density distributions.

Two Stable Phosphorus-Containing Four-Membered Ring Radical Cations with Inverse Spin Density Distributions

2014 ◽  
Vol 136 (17) ◽  
pp. 6251-6254 ◽  
Author(s):  
Yuanting Su ◽  
Xin Zheng ◽  
Xingyong Wang ◽  
Xuan Zhang ◽  
Yunxia Sui ◽  
...  
Keyword(s):  
Spin Density ◽  
Radical Cations ◽  
Membered Ring ◽  
Density Distributions ◽  
Phosphorus Containing

Computational Investigation of the Asymmetry in Photosynthetic Reaction Center Models from First Principles

2020 ◽  
Author(s):  
Denis Artiukhin ◽  
Patrick Eschenbach ◽  
Johannes Neugebauer
Keyword(s):  
Spin Density ◽  
Reaction Center ◽  
Density Functional ◽  
Photosynthetic Reaction Center ◽  
Chem Phys ◽  
Molecular Structures ◽  
Error Characteristic ◽  
Molecular Systems ◽  
Density Distributions ◽  
The Asymmetry

We present a computational analysis of the asymmetry in reaction center models of photosystem I, photosystem II, and bacteria from <i>Synechococcus elongatus</i>, <i>Thermococcus vulcanus</i>, and <i>Rhodobacter sphaeroides</i>, respectively. The recently developed FDE-diab methodology [J. Chem. Phys., 148 (2018), 214104] allowed us to effectively avoid the spin-density overdelocalization error characteristic for standard Kohn–Sham Density Functional Theory and to reliably calculate spin-density distributions and electronic couplings for a number of molecular systems ranging from dimeric models in vacuum to large protein including up to about 2000 atoms. The calculated spin densities showed a good agreement with available experimental results and were used to validate reaction center models reported in the literature. We demonstrated that the applied theoretical approach is very sensitive to changes in molecular structures and relative orientation of molecules. This makes FDE-diab a valuable tool for electronic structure calculations of large photosynthetic models effectively complementing the existing experimental techniques.

A Combined ab initio and Density Functional Study of the Electronic Structure of Thymine and 2-Thiothymine Radicals

2003 ◽  
Vol 68 (12) ◽  
pp. 2322-2334 ◽  
Author(s):  
Robert Vianello ◽  
Zvonimir B. Maksić
Keyword(s):  
Ab Initio ◽  
Spin Density ◽  
Density Functional ◽  
Radical Cations ◽  
Functional Study ◽  
Theory Approach ◽  
Functional Theory ◽  
Adiabatic Ionization Potential ◽  
Highest Occupied Molecular Orbital ◽  
Positively Charged

The electronic and energetic properties of thymine (1) and 2-thiothymine (2) and their neutral and positively charged radicals are considered by a combined ab initio and density functional theory approach. It is conclusively shown that ionization of 1 and 2 greatly facilitates deprotonation of the formed radical cations thus making the proton transfer between charged and neutral precursor species thermodynamically favourable. The adiabatic ionization potential of 1 and 2 are analysed. It appears that ADIP(1) is larger than ADIP(2) by 10 kcal/mol, because of greater stability of the highest occupied molecular orbital (HOMO) of the former. It is also shown beyond any doubt that the spin density in neutral and cationic radical of 2 is almost exclusively placed on the σ-3p AO of sulfur implying that these two systems represent rather rare sigma-radicals. In contrast, the spin density of radicals of 1 is distributed over their π-network.

Mono(arene) Complexes of Thallium(I) Supported by a Weakly Coordinating Anion

2007 ◽  
Vol 26 (7) ◽  
pp. 1811-1815 ◽  
Author(s):  
Yann Sarazin ◽  
Nikolas Kaltsoyannis ◽  
Joseph A. Wright ◽  
Manfred Bochmann
Keyword(s):  
Arene Complexes ◽  
Weakly Coordinating ◽  
Weakly Coordinating Anion

Density functional theory study on the structural, reactivity, and electronic properties of all mono-, di-, tri-, tetra-, and penta-fluoroanilines as monomers for conducting polymers

2012 ◽  
Vol 90 (10) ◽  
pp. 902-914 ◽  
Author(s):  
Hossein Shirani Il Beigi
Keyword(s):  
Density Functional Theory ◽  
Conducting Polymers ◽  
Structural Properties ◽  
Density Functional ◽  
Dipole Moments ◽  
Radical Cations ◽  
The Other ◽  
Functional Theory ◽  
Density Distributions ◽  
Electric Polarizabilities

Electrical and structural properties of mono-, di-, tri-, tetra-, and penta-fluoroanilines as candidate monomers for new conducting polymers have been investigated using hybrid density functional theory (B3LYP/6–311+G**) based methods. The effects of the number and position of the fluorine atoms on the electrical and structural properties of fluoroanilines and their radical cations have also been investigated. The values of the vibrational frequencies, charge and spin-density distributions, ionization potentials, dipole moments, electric polarizabilities, HOMO-LUMO gaps, and the NICS values of these compounds have been calculated and analyzed as well. The results showed that the double bonds in 2-fluoroaniline and 2,5-difluoroaniline are more delocalized compared with other fluoroanilines; therefore, these molecules have the most aptitude for the electropolymerization reactions. The frequency analysis showed that the electrochemical stability of 2-fluoroaniline is greater than the other fluoroanilines. Also, this molecule possesses the largest NICS value compared to the other fluoroanilines. Consequently, 2-fluoroaniline has the largest ring current and the highest conductivity among all other monomers. Based on the results obtained, 2-fluoroaniline and 2,5-difluoroaniline are the best candidate monomers among all fluoroanilines for the synthesis of corresponding conducting polymers.

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