Structural, electronic and optical properties of novel carbonate fluorides ABCO3F (A=K, Rb, Cs; B=Ca, Sr)

Rao, E. Narsimha; Appalakondaiah, S.; Yedukondalu, N.; Vaitheeswaran, G.

doi:10.1016/j.jssc.2014.01.029

Cited by 22 publications

(10 citation statements)

References 41 publications

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“…The corresponding results show the following increment order: Δ n (6) > Δ n (8) > Δ n (7) > Δ n (9). Moreover, these values except for that of compound 9 are found to be closer to the well-known nonlinear crystal DAST (0.39, 0.55, and 0.64) and higher than recently reported carbonate fluoride crystals ABCO 3 F (A = K, Rb, Cs; B = Ca, Sr, Pb) (Δ n around 0.1056, 0.0887, 0.0921, 0.0966) crystal birefringence values, − which clearly indicates that the studied noncentrosymmetric explosive compounds may possess good phase matching applications in visible and near-IR regions. Further analyses on frequency-dependent second-harmonic response of these compounds will be useful in phase transition, sensitivity correlation studies, and designing new organic nonlinear optical materials in near future.…”

Section: Resultssupporting

confidence: 76%

Time-Domain Terahertz Spectroscopy and Density Functional Theory Studies of Nitro/Nitrogen-Rich Aryl-Tetrazole Derivatives

et al. 2020

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The paper reports the time-domain THz spectroscopy studies of noncentrosymmetric energetic nitro/ nitrogen-rich aryl-tetrazole high-energy molecules. The fingerprint spectra in the THz domain reveal the role of different functional groups attached to position "1" of the tetrazole moiety, which controls the energetic properties. These responses are deliberated through density functional theory (DFT) calculations. The synthesized aryl-tetrazoles exhibit high positive heat of formation (369−744 kJ/mol), high detonation velocities, and pressures (D v : 7734−8298 m·s −1 ; D p : 24−28 GPa) in comparison to the noncentrosymmetric 2,4,6-trinitrotoluene (TNT). These compounds exhibit variation in the refractive indices and absorption between 0.1 and 2.2 THz range. The DFT studies at the molecular and single-crystal level (using plane wave pseudo potential method) endorse in detecting these bands (with ∼1% deviation). The calculated vibrational frequencies and linear optical properties are found to have good agreement with the experimental data in UV−visible and THz regions.

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Section: Resultssupporting

confidence: 76%

Time-Domain Terahertz Spectroscopy and Density Functional Theory Studies of Nitro/Nitrogen-Rich Aryl-Tetrazole Derivatives

et al. 2020

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“…Importantly, we noticed that K 2 BDAF has an almost similar birefringence value when compared to DAST (0.39, 0.55, 0.64) and DSTMS (0.45, 0.63) . With increased curiosity and to have a different comparison, we have calculated the Δ n values for KCaCO 3 F, KSrCO 3 F, RbSrCO 3 F, and CsPbCO 3 F crystals using our previously reported results and resultant spectra are shown along with K 2 DNABT and K 2 BDAF in Figure . It is clear from the plots that the birefringence of K 2 BDAF and K 2 DNABT is much higher than that for all the carbonate fluoride nonlinear crystals (KCa (0.09), KSr (0.09), RbSr (0.08), CsPb (0.10)).…”

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 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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“…In recent years, our laboratory has been focused on the study and design of new NLO crystals in the fluoride carbonate family. A new series of fluoride carbonate crystals have been synthesized, including ABCO 3 F (A = K, Rb, Cs; B = Ca, Sr, Ba), Na 8 Lu 2 (CO 3 ) 6 F 2 , and Na 3 Lu(CO 3 ) 2 F 2 , K 2.70 Pb 5.15 (CO 3 ) 5 F 3 , RbPbCO 3 F, CsPbCO 3 F, , and RbMgCO 3 F, which are verified to be very promising for UV NLO materials with a wide transparency for practical applications by experimental measurements and theoretical calculation. , In addition, transition metal fluoride carbonates, KCuCO 3 F, BaMCO 3 F 2 (M = Mn, Cu, and Zn), , and Ba 2 Co(CO 3 ) 2 F 2 have also been discovered, among which only KCuCO 3 F is both NCS and polar, and the others are centrosymmetric.…”

Section: Introductionmentioning

confidence: 91%

Structural Modulation of Anionic Group Architectures by Cations to Optimize SHG Effects: A Facile Route to New NLO Materials in the ATCO₃F (A = K, Rb; T = Zn, Cd) Series

Yang

Peng

et al. 2015

Chem. Mater.

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Structural, electronic and optical properties of novel carbonate fluorides ABCO3F (A=K, Rb, Cs; B=Ca, Sr)

Cited by 22 publications

References 41 publications

Time-Domain Terahertz Spectroscopy and Density Functional Theory Studies of Nitro/Nitrogen-Rich Aryl-Tetrazole Derivatives

Time-Domain Terahertz Spectroscopy and Density Functional Theory Studies of Nitro/Nitrogen-Rich Aryl-Tetrazole Derivatives

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

Structural Modulation of Anionic Group Architectures by Cations to Optimize SHG Effects: A Facile Route to New NLO Materials in the ATCO₃F (A = K, Rb; T = Zn, Cd) Series

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Structural, electronic and optical properties of novel carbonate fluorides ABCO3F (A=K, Rb, Cs; B=Ca, Sr)

Cited by 22 publications

References 41 publications

Time-Domain Terahertz Spectroscopy and Density Functional Theory Studies of Nitro/Nitrogen-Rich Aryl-Tetrazole Derivatives

Time-Domain Terahertz Spectroscopy and Density Functional Theory Studies of Nitro/Nitrogen-Rich Aryl-Tetrazole Derivatives

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

Structural Modulation of Anionic Group Architectures by Cations to Optimize SHG Effects: A Facile Route to New NLO Materials in the ATCO3F (A = K, Rb; T = Zn, Cd) Series

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Structural Modulation of Anionic Group Architectures by Cations to Optimize SHG Effects: A Facile Route to New NLO Materials in the ATCO₃F (A = K, Rb; T = Zn, Cd) Series