Role of spin–orbit interaction on the nonlinear optical response of CsPbCO<sub>3</sub>F using DFT

Rao, E. Narsimha; Vaitheeswaran, G.; Reshak, A.H.; Auluck, S.

doi:10.1039/c7cp05750d

Cited by 25 publications

(12 citation statements)

References 53 publications

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“…Therefore, accurate prediction of electronic band structure of an energetic materials plays a crucial role in understanding their photo decomposition process. Many impact sensitivity versus electronic band gap correlation studies of explosives are reported in the literature with a conclusion that lower band gap materials are highly sensitive to impact. , Moreover, the complex second-order nonlinear optical susceptibility tensor is very sensitive to energy gap value. − Therefore, it is crucial to obtain an accurate band gap of the chosen materials. In view of these important correlations, we have calculated the electronic band structure of K 2 BDAF using different exchange correlation functionals (LDA, GGA(PBE, PBEsol), default TB-mBJ, and new parametrized TB-mBJ) to predict the accurate band gap using full-potential linearized augmented plane wave (FP-LAPW) method .…”

Section: Resultsmentioning

confidence: 99%

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Structure–Property Correlation Studies of Potassium 4,4′-Bis(dinitromethyl)-3,3′-azofurazanate: A Noncentrosymmetric Primary Explosive

Rao

Vaitheeswaran

2019

J. Phys. Chem. C

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The knowledge of mechanical, vibrational, electronic properties, and origin of polarizability of a noncentrosymmetric explosive materials plays a crucial role in understanding the phase transition mechanism and stand-off detection of high energy material (HEM) residues on the surfaces and interfaces. In the present study, we have explored the role of crystal structure and chemical composition in predicting the structural, dynamical, electronic, and optical properties of two newly synthesized noncentrosymmetric green primary explosives, potassium 4,4′-bis(dinitromethyl)-3,3′-azofurazanate (K 2 BDAF) and potassium 1,1′-dinitramino-5,5′-bistetrazolate (K 2 DNABT), using density functional theory simulations. The calculated structural and mechanical properties suggest that K 2 BDAF and K 2 DNABT are mechanically stable and possess lower bulk modulus values [K 2 BDAF (18.91 GPa) < K 2 DNABT (22.4 GPa)] than toxic lead azide Pb(N 3 ) 2 (26 GPa). The Born effective charge (BEC) and vibrational, thermodynamic, and phonon dispersion studies reveals that both crystals are dynamically stable and that K 2 BDAF is found to be more stable, more polarizable, and easily detectable than K 2 DNABT. The TB-mBJ electronic band structure study reveals that K 2 BDAF is an indirect band gap (along R → V high symmetry points) material with a gap of 2.37 eV < K 2 DNABT (3.57 eV, direct). The density of states and charge density plots show that both crystals possess mixed covalent and ionic bonding nature, and these results are consistent with BEC analysis. The nitrogen, oxygen and carbon p states are found to be dominant near the Fermi level in the valence band. From the optical properties study, it is found that the studied explosive materials have the lowest dielectric constant compared with the well-known 4-N,N-dimethylamino-4-N-methylstilbazolium tosylate (DAST) crystal, i.e., K 2 DNABT (2.68) < K 2 BDAF (2.91) < DAST (5.2), and show birefringence similar to (K 2 BDAF static value, 0.32; at 532 nm, 0.58), (K 2 DNABT static value, 0.25; at 532 nm, 0.27) that of DAST (0.39, 0.55, 0.64) and 4-N,Ndimethylamino-4′-N′-methylstilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS) (0.45, 0.63) NLO crystals. For both the studied explosives, the absorption is found to be strong in the [010] direction and follows the relation α(K 2 BDAF) < α(K 2 DNABT). The analysis of differences in BEC reveals that from K 2 DNABT to K 2 BDAF, the positive contribution of atoms to total birefringence increases as follows: K1 (0.09559), O1 (0.69236), O2 (0.77962), N1 (1.41018), N2 (0.92394), N3 (0.27415), N4 (0.74264), and N5 (0.84502). The negative contribution from C1 is increased by −1.29582. Over all, our results are in agreement with the experimentally reported sensitivity trend, and the reasons behind the sensitivity differences of K 2 DNABT and K 2 BDAF are explored.

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Section: Resultsmentioning

confidence: 99%

“…Calculated birefringence of K 2 BDAF and K 2 DNABT at experimental crystal structure volume. Results are compared with KCaCO 3 F, KSrCO 3 F, RbSrCO 3 F, and CsPbCO 3 F (with and without spin–orbit effects) …”

Section: Resultsmentioning

confidence: 99%

Structure–Property Correlation Studies of Potassium 4,4′-Bis(dinitromethyl)-3,3′-azofurazanate: A Noncentrosymmetric Primary Explosive

Rao

Vaitheeswaran

2019

J. Phys. Chem. C

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“…The electronic properties were evaluated using the mBJ-GGA potentials with consideration of the spin-orbit coupling (SOC) interaction. − The calculated band gap with SOC was corrected to match the experimental values using the alloy formula. − The basis function was expanded to R mt × K max = 9, where R mt represents the smallest muffin-tin radius of all the microscopic spheres in the unit cell, and K max represents the plane-wave cutoff. The wave functions in the muffin-tin spheres were expanded to l max = 10.…”

Section: Methodsmentioning

confidence: 99%

Anion Substitution Effects on the Structural, Electronic, and Optical Properties of Inorganic CsPb(I_1–xBr_x)₃ and CsPb(Br_1–xCl_x)₃ Perovskites: Theoretical and Experimental Approaches

et al. 2021

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Several inorganic perovskites of iodine, bromine, and chlorine halides have emerged as candidates for various optoelectronic devices. Highquality CsPb(I 1−x Br x ) 3 and CsPb(Br 1−x Cl x ) 3 (x = 0.00, 0.25, 0.50, 0.75, and 1.00) inorganic perovskite thin films were prepared in this study using a thermal evaporation system. Experiments and first-principles calculations were conducted to elucidate the structural, electronic, and optical properties of the prepared films at room temperature. The thin-film perovskite band gap was tuned from 1.85 to 3.13 eV by replacing I − with Br − and then Cl − . Dominant excitonic effects on the onset of optical absorption led us to explicitly account for enhancing absorption through the Sommerfield factor, enabling us to extract the electronic band gap and the exciton binding energy correctly. We correlated our experimental results with the theory of first principles and gained insight into the lattice parameters, electronic structure, excitonic binding energy (E b ), dielectric constant (ε), and reduced effective mass (μ) of the carriers. With increasing concentration (x) of Br and Cl, the E b increased from 39.44 meV for pure CsPbI 3 to 63.04 and 96.73 meV for pure CsPbBr 3 and CsPbCl 3 , respectively, because of a decrease in the dielectric constant and the almost constant value of μ at ∼0.051 m e . The Urbach energy (E U ) was calculated and found to fluctuate between 28 and 77 meV.

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“…The mixed inorganic perovskite structures were created by building a 1 × 1 × 2 supercell with a binary perovskite’s Pnma space group. Because of the presence of a heavy element (Pb) in the structure, the SOC interaction − ,, was used with mBJ-GGA, as described in our previous work . To match the experimental values, the calculated band gap with SOC was corrected by using the alloy formula. ,, During the calculation, RK max = 9 and k -points = 100 were used, and the total energy was converged to 10 –4 Ry.…”

Section: Methodsmentioning

confidence: 99%

Density Functional Theory Analysis of Structural, Electronic, and Optical Properties of Mixed-Halide Orthorhombic Inorganic Perovskites

et al. 2021

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Inorganic metal-halide perovskites hold a lot of promise for solar cells, light-emitting diodes, and lasers. A thorough investigation of their optoelectronic properties is ongoing. In this study, the accurate modified Becke Johnson generalized gradient approximation (mBJ-GGA) method without/with spin orbital coupling (SOC) implemented in the WIEN2k code was used to investigate the effect of mixed I/Br and Br/Cl on the electronic and optical properties of orthorhombic CsPb(I1–x Br x )3 and CsPb(Br1–x Cl x )3 perovskites, while the Perdew–Burke–Ernzerhof generalized gradient approximation (PBE-GGA) method was used to investigate their structural properties. The calculated band gap (E g) using the mBJ-GGA method was in good agreement with the experimental values reported, and it increased clearly from 1.983 eV for CsPbI3 to 2.420 and 3.325 eV for CsPbBr3 and CsPbCl3, respectively. The corrected mBJ + SOC E g value is 1.850 eV for CsPbI3, which increased to 2.480 and 3.130 eV for CsPbBr3 and CsPbCl3, respectively. The calculated photoabsorption coefficients show a blue shift in absorption, indicating that these perovskites are suitable for optical and optoelectronic devices.

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Role of spin–orbit interaction on the nonlinear optical response of CsPbCO₃F using DFT

Cited by 25 publications

References 53 publications

Structure–Property Correlation Studies of Potassium 4,4′-Bis(dinitromethyl)-3,3′-azofurazanate: A Noncentrosymmetric Primary Explosive

Structure–Property Correlation Studies of Potassium 4,4′-Bis(dinitromethyl)-3,3′-azofurazanate: A Noncentrosymmetric Primary Explosive

Anion Substitution Effects on the Structural, Electronic, and Optical Properties of Inorganic CsPb(I_1–xBr_x)₃ and CsPb(Br_1–xCl_x)₃ Perovskites: Theoretical and Experimental Approaches

Density Functional Theory Analysis of Structural, Electronic, and Optical Properties of Mixed-Halide Orthorhombic Inorganic Perovskites

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Role of spin–orbit interaction on the nonlinear optical response of CsPbCO3F using DFT

Cited by 25 publications

References 53 publications

Structure–Property Correlation Studies of Potassium 4,4′-Bis(dinitromethyl)-3,3′-azofurazanate: A Noncentrosymmetric Primary Explosive

Structure–Property Correlation Studies of Potassium 4,4′-Bis(dinitromethyl)-3,3′-azofurazanate: A Noncentrosymmetric Primary Explosive

Anion Substitution Effects on the Structural, Electronic, and Optical Properties of Inorganic CsPb(I1–xBrx)3 and CsPb(Br1–xClx)3 Perovskites: Theoretical and Experimental Approaches

Density Functional Theory Analysis of Structural, Electronic, and Optical Properties of Mixed-Halide Orthorhombic Inorganic Perovskites

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Role of spin–orbit interaction on the nonlinear optical response of CsPbCO₃F using DFT

Anion Substitution Effects on the Structural, Electronic, and Optical Properties of Inorganic CsPb(I_1–xBr_x)₃ and CsPb(Br_1–xCl_x)₃ Perovskites: Theoretical and Experimental Approaches