scholarly journals The Mechanism of the Propagation in the Anionic Polymerization of Polystyryllithium in Non-Polar Solvents Elucidated by Density Functional Theory Calculations. A Study of the Negligible Part Played by Dimeric Ion-Pairs under Usual Polymerization Conditions

Polymers ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 1022
Author(s):  
Hideo Morita ◽  
Marcel Van Beylen
Keyword(s):  
Density Functional Theory ◽  
Transition State ◽  
Anionic Polymerization ◽  
Density Functional ◽  
Ion Pairs ◽  
Density Functional Theory Calculations ◽  
Dft Method ◽  
Functional Theory ◽  
Elementary Processes ◽  
Rate Of Reaction

The elementary processes occurring in the anionic polymerization of styrene with dimerically associated polystyryllithium (propagation during the anionic polymerization of dimeric polystyryllithium) in the gas phase and cyclohexane were studied using MX062X/6-31+G(d), a recently developed density functional theory (DFT) method and compared with the polymerization of styrene with non-associated polystyryllithium, which was described in a previous study. The most stable transition state in the reaction of styrene with dimeric polystyryllithium has a structure in which the side chains of styrene and the two chain end units of polystyryllithium are located in the same direction around the Li atom near the reactive site. The relative enthalpy for this transition state in cyclohexane is 28 kJ·mol−1, which is much lower than that for the reaction of non-associated polystyryllithium (51 kJ·mol−1). However, the relative free energy (which determines the rate constant) for the former is 93 kJ·mol−1, which is greater than that for the latter by 7 kJ·mol−1, indicating that the latter reaction (reaction with non-associated polystyryllithium) is advantageous over the former (reaction with dimeric polystyrylllithium). Their rates of reaction are also affected by initiator concentrations; in the case of reactions with low initiator concentrations, from which high molecular weight polymers are usually obtained, the rate of reaction corresponding to non-associated polystyryllithium is much larger than that corresponding to dimeric polystyryllithium.

scholarly journals Substituent effects in the decarboxylation reactions of coordinated arylcarboxylates in dinuclear copper complexes, [(napy)Cu2(O2CC6H4X)]+

2017 ◽  
Vol 23 (6) ◽  
pp. 351-358 ◽  
Author(s):  
Qiuyan Jin ◽  
Jiaye Li ◽  
Alireza Ariafard ◽  
Allan J Canty ◽  
Richard AJ O’Hair
Keyword(s):  
Density Functional Theory ◽  
Transition State ◽  
Density Functional ◽  
Copper Complexes ◽  
Substituent Effects ◽  
Density Functional Theory Calculations ◽  
Molecular Formula ◽  
Binuclear Complexes ◽  
Aryl Group ◽  
Functional Theory

A combination of gas-phase ion trap mass spectrometry experiments and density functional theory (DFT) calculations have been used to examine the role of substituents on the decarboxylation of 25 different coordinated aromatic carboxylates in binuclear complexes, [(napy)Cu2(O2CC6H4X)]+, where napy is the ligand 1,8-naphthyridine (molecular formula, C8H6N2) and X = H and the ortho ( o), meta ( m) and para ( p) isomers of F, Br, CN, NO2, CF3, OAc, Me and MeO. Two competing unimolecular reaction pathways were found: decarboxylation to give the organometallic cation [(napy)Cu2(C6H4X)]+ or loss of the neutral copper benzoate to yield [(napy)Cu]+. The substituents on the aryl group influence the branching ratios of these product channels, but decarboxylation is always the dominant pathway. Density functional theory calculations reveal that decarboxylation proceeds via two transition states. The first enables a change in the coordination mode of the coordinated benzoate in [(napy)Cu2(O2CC6H4X)]+ from the thermodynamically favoured O, O-bridged form to the O-bound form, which is the reactive conformation for the second transition state which involves extrusion of CO2 with concomitant formation of the CO2 coordinated organometallic cation, [(napy)Cu2(C6H4X)(CO2)]+, which then loses CO2 in the final step to yield [(napy)Cu2(C6H4X)]+. In all cases the barrier is highest for the second transition state. The o-substituted benzoates show a lower activation energy than the m-substituted ones, while the p-substituted ones have the highest energy, which is consistent with the experimentally determined normalised collision energy required to induce fragmentation of [(napy)Cu2(O2CC6H4X)]+.

Density functional theory prediction for the second-order nonlinear optical responses of phenanthroline-fused phthalocyanine derivatives

2014 ◽  
Vol 18 (01n02) ◽  
pp. 58-66 ◽  
Author(s):  
Chao Chen ◽  
Lijuan Zhang ◽  
Luyang Zhao ◽  
Dongdong Qi ◽  
Jianzhuang Jiang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Rayleigh Scattering ◽  
Electronic Absorption Spectra ◽  
Density Functional Theory Calculations ◽  
Dft Method ◽  
Second Order ◽  
Absorption Region ◽  
Functional Theory ◽  
Optical Responses

A series of unsymmetrical phenanthroline-fused phthalocyanine derivatives including Zn [ Pc ( Phen )], Zn [ Pc ( Phen )2], Zn [ Pc ( Phen )3], Zn [ Pc ( NH 2)6( Phen )], Zn [ Pc ( NH 2)4( Phen )2], Zn [ Pc ( NH 2)2( Phen )3], Zn [ PcF 6( Phen )], Zn [ PcF 4( Phen )2], and Zn [ PcF 2( Phen )3] were designed to explore their properties of geometric and electronic structures, electronic absorption spectra, and second-order nonlinear responses under density functional theory and time-dependent density functional theory calculations. The computational results show that the peripheral substituents with push-pull effect could obviously change the π–π* transitions, leading to a tunable absorption region in the range between 300–800 nm. The hyperpolarizabilities were carefully investigated using CP-DFT method, revealing the size effect and clarifying the limit when expanding the conjugated system is employed to improve the hyper-Rayleigh scattering response coefficient (βHRS). According to the results, the NH 2-substitued phenanthroline-fused phthalocyanines are considered as ideal NLO blocking materials with large βHRS.

Is a Non-Transition Element Nitride Ferromagnet Ever Achievable? Indication of the N-N Pairing Instability

2006 ◽  
Vol 71 (11-12) ◽  
pp. 1525-1531 ◽  
Author(s):  
Wojciech Grochala
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Transition Element ◽  
Density Functional Theory Calculations ◽  
Functional Theory

The enthalpy of four polymorphs of CaN has been scrutinized at 0 and 100 GPa using density functional theory calculations. It is shown that structures of diamagnetic calcium diazenide (Ca2N2) are preferred over the cubic ferromagnetic polymorph (CaN) postulated before, both at 0 and 100 GPa.

scholarly journals Tensor-structured algorithm for reduced-order scaling large-scale Kohn–Sham density functional theory calculations

2021 ◽  
Vol 7 (1) ◽  
Author(s):  
Chih-Chuen Lin ◽  
Phani Motamarri ◽  
Vikram Gavini
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Large Scale ◽  
Density Functional Theory Calculations ◽  
System Size ◽  
Real Space ◽  
Functional Theory ◽  
Reduced Order ◽  
Separable Approximation ◽  
Tensor Basis

AbstractWe present a tensor-structured algorithm for efficient large-scale density functional theory (DFT) calculations by constructing a Tucker tensor basis that is adapted to the Kohn–Sham Hamiltonian and localized in real-space. The proposed approach uses an additive separable approximation to the Kohn–Sham Hamiltonian and an L1 localization technique to generate the 1-D localized functions that constitute the Tucker tensor basis. Numerical results show that the resulting Tucker tensor basis exhibits exponential convergence in the ground-state energy with increasing Tucker rank. Further, the proposed tensor-structured algorithm demonstrated sub-quadratic scaling with system-size for both systems with and without a gap, and involving many thousands of atoms. This reduced-order scaling has also resulted in the proposed approach outperforming plane-wave DFT implementation for systems beyond 2000 electrons.

Sign in / Sign up

Export Citation Format

Share Document