Theoretical studies on structures and nonlinear optical properties of alkali doped electrides B<sub>12</sub>N<sub>12</sub>-M (M = Li, Na, K)

Hou, Na; Wu, Yuanyuan; Liu, Jiayuan

doi:10.1002/qua.25177

Cited by 34 publications

(20 citation statements)

References 46 publications

(39 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The significance of this σ‐hole bonding has been established in the broad domain of rational drug design, anion recognition, synthesis of new material, biochemistry, and other fields [9–12] . With the rapid increase in studies concerned with σ‐hole, it was realized that the depletion of electron density lies not only along the extensions of the covalent bonds, but can also be present above a planar molecule (SO 3 ) or planar groups (of a molecule) such as −NO 2 , phenyl and carbonyl [13–17] . Generally, this positive electrostatic potential lies in an area perpendicular to an atom or group (from a molecule) or on the centroid of aromatic ring.…”

Section: Introductionmentioning

confidence: 99%

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

et al. 2021

View full text Add to dashboard Cite

A theoretical study has been carried out on the π‐hole based chalcogen bonding interaction between SO3 and various pyridines (XC5H4N), at the MP2=full/aug‐cc‐pVTZ level, to obtain a better insight into the nature and strength of N…S bond. Our calculations predict two different types of chalcogen bonded complexes: (1) Type‐A complex is formed via lone pair‐ π‐hole (N…S) interaction, and (2) Type‐B complex is stabilized through π‐hole‐π‐electron interaction. The binding energy of the Type‐A complexes varies between −109.78 and ‐81.56 kJ/mol whereas it ranges between −28.93 and −17.82 kJ/mol for Type‐B complexes. The nature of the N…S bond and the changes in its properties on the influence of electron donating and electron withdrawing substituents have been discussed with the help of various computational tools like AIM, NCI, SAPT and NBO analysis. The binding energy of the Type‐A complexes are found to correlate with the basicity parameters such as PA and Vs,min of the substituted pyridines. The binding energies of the pyridine complexes with SF2, SO2, CS2 and OCS are also computed for finding the effect of variation of Vs,max value of the S‐atom on the binding energy. The 2nd order hyperconjugation interaction energy between LP(N) and σ*(S−O)/LP*(S) is well correlated to the binding energy as: −ΔE=0.11E(2) −20.08. The variation in the bond distances and their corresponding vibrational frequencies of both the interacting partners (XC5H4N and SO3) are discussed in detail.

show abstract

Section: Introductionmentioning

confidence: 99%

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Alkali metals have low ionization potential, therefore valence electrons from these metal atoms are easily diffused out to act as excess electrons in materials. This technique is being frequently used to design high performance [41] NLO materials. Literature reveals that lithium doping on B10H14 framework leads to considerable increase in hyperpolarizability (2.31×10 4 au) because of diffused excess electrons of Li atom [42].…”

Section: Introductionmentioning

confidence: 99%

A New Strategy of bi-Alkali Metal Doping to Design Boron Phosphide Nanocages of High Nonlinear Optical Response with Better Thermodynamic Stability

Baloach

Ayub

Mahmood

et al. 2021

J Inorg Organomet Polym

View full text Add to dashboard Cite

Nonlinear optical materials possess high rank in fields of optics owing to their impacts, utilization and extended applications in industrial sector. Therefore, design of molecular systems with high nonlinear optical response along with high thermodynamic stability is a dire need of this era. Hence, the present study involves investigation of bi-alkali metal doped boron phosphide nanocages M2@B12P12 (M=Li, Na, K) in search of stable nonlinear optical materials.The investigation includes execution of geometrical and opto-electronic properties of complexes by means of density functional theory (DFT) computations. Bi-doped alkali metal atoms introduce excess of electrons in the host B12P12 nanocage. These electrons contribute towards the formation of new HOMO, thus reducing HOMO-LUMO gaps. The reduced HOMO-LUMO gap ranges from 0.63eV to 3.69eV. The diffused excess electrons also come up with increased hyperpolarizability values of complexes i.e. up to 4.0×10 4 au. TD-DFT calculations have been performed to examine crucial transition states and for UV-VIS analysis.IR and DOS spectra have been plotted to support our obtained results. Non covalent interaction (NCI) calculations along with quantum theory of the atoms in molecules (QTAIM) analysis were carried out to understand the bonding interactions between alkali metal atoms and B12P12 nanocage. All obtained results suggest bi-alkali metal doped nanocages as exceptionally stable materials with improved NLO response and superb candidates for their vast applications in optics.

show abstract

“…Also, from the geometrical point of view, a larger OCO angle is expected for a stronger interaction between CO 2 and the anions, because of the rehybridization that takes place in the carbon atom. These electronic and geometrical parameters have been reported to correlate with the anion/CO 2 bond strength [38, 39].…”

Section: Thermodynamics Of the Anions/co2 Reactions In The Gas Phasementioning

confidence: 99%

MP2 versus density functional theory calculations in CO₂‐sequestration reactions with anions: Basis set extrapolation and solvent effects

Quattrociocchi

Oliveira

Carneiro

et al. 2020

Int J of Quantum Chemistry

View full text Add to dashboard Cite

The emission of carbon dioxide in large amounts is commonly believed to be the main cause of global climate changes. Development of CO2 capture processes is still a big current challenge. Some anions have been studied for the gas sequestration process due their great affinity to CO2. In this work, electronic structure calculations were performed at the MP2/aug‐cc‐pvtz level to compute the interaction between 20 anions and CO2. A complete basis set scheme, using extrapolated energies, was also employed for both gas phase and solvent calculations. The reactions between the anions and CO2 were therefore studied in four different conditions (gas phase, toluene, tetrahydrofuran and water). The trends observed for the reaction thermodynamics with the MP2 method is similar to that observed previously with the B3LYP‐D3 and M06‐2X functionals. The reactions in the gas phase are highly exothermic and do not involve any activation energy. The solvent effect reduces the exothermicity and induces an intrinsic activation barrier. The negative charge is dispersed in the adduct, leading to a weaker interaction in a polar solvent. Then, increasing the medium polarity, the energy difference between the adduct and the reactants decreases. We also observed a limit for solvent stabilization in the low dielectric constant range. For example, the results obtained with tetrahydrofuran are closer to those obtained with water than to those obtained with toluene. Considering both the thermodynamics of the reaction and the differential solvent effects, we were able to indicate anions derived from alkyl sulfides as the most convenient for CO2 sequestration among the set here considered.

show abstract

Theoretical studies on structures and nonlinear optical properties of alkali doped electrides B₁₂N₁₂-M (M = Li, Na, K)

Cited by 34 publications

References 46 publications

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

A New Strategy of bi-Alkali Metal Doping to Design Boron Phosphide Nanocages of High Nonlinear Optical Response with Better Thermodynamic Stability

MP2 versus density functional theory calculations in CO₂‐sequestration reactions with anions: Basis set extrapolation and solvent effects

Contact Info

Product

Resources

About

Theoretical studies on structures and nonlinear optical properties of alkali doped electrides B12N12-M (M = Li, Na, K)

Cited by 34 publications

References 46 publications

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO3 Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO3 Molecule

A New Strategy of bi-Alkali Metal Doping to Design Boron Phosphide Nanocages of High Nonlinear Optical Response with Better Thermodynamic Stability

MP2 versus density functional theory calculations in CO2‐sequestration reactions with anions: Basis set extrapolation and solvent effects

Contact Info

Product

Resources

About

Theoretical studies on structures and nonlinear optical properties of alkali doped electrides B₁₂N₁₂-M (M = Li, Na, K)

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

MP2 versus density functional theory calculations in CO₂‐sequestration reactions with anions: Basis set extrapolation and solvent effects