Effect of bromine deficiency on the lattice dynamics and dielectric properties of alpha-phase diisopropylammonium bromide molecular crystals

Ahmad Alsaad, Chris M. Marin, Nabil Alaqtash, Hsien Wen Chao, Tsun Hsu Chang, Chin Li "Barry" Cheung, A. Ahmad, I. A. Qattan, Renat F Sabirianov

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Diisopropylammonium bromide (DIPAB) molecular ferroelectric crystals were synthesized and examined to exhibit a large electric polarization (∼23μC/cm2), a large dielectric constant in the α-phase. Although the PXRD pattern indicates that the α-DIPAB sample has an overall excellent crystallinity, our analysis of its FT-IR and Raman vibrational spectra suggests the presence of disorder in the synthesized crystals as indicated by the presence of broad features in the Raman spectrum. Using vdW+DF2 calculations, we identified the majority of vibrational modes in the experimental spectra and analyzed the ones due to Br-disorder. We found that the bromine (Br) deficiency strongly affects the electric properties of α-DIPAB. Particularly, the experimentally measured dielectric constant of α-DIPAB is large (∼20), whereas the DFT-based calculations of the ideal DIPAB give much smaller values (∼2-3). We find that Br-deficiency is responsible for large dielectric constant of the DIPAB crystal with calculated value of ∼15-20. Furthermore, we showed that the van der Waals forces have a slight effect on the structural parameters, only causing a small shift in the vibrational frequencies. The main vibrational features of the DIPAB crystal in the Raman spectrum were shown to be driven by covalent bonding in the DIPA molecules and hydrogen bonds between the molecules with Br.

Original languageEnglish (US)
Pages (from-to)82-85
Number of pages4
JournalJournal of Physics and Chemistry of Solids
Volume113
DOIs
StatePublished - Feb 1 2018

Fingerprint

Molecular crystals
Bromine
Lattice vibrations
bromine
Bromides
Dielectric properties
dynamic characteristics
dielectric properties
bromides
Crystals
Permittivity
Vibrational spectra
crystals
Raman scattering
Van der Waals forces
Molecules
permittivity
Raman spectra
Discrete Fourier transforms
Ferroelectric materials

Keywords

  • Alpha-phase diisopropylammonium bromide
  • Bromine deficiency
  • Dielectric properties
  • FT-IR and Raman vibrational spectra
  • Lattice dynamics

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Effect of bromine deficiency on the lattice dynamics and dielectric properties of alpha-phase diisopropylammonium bromide molecular crystals. / Alsaad, Ahmad; Marin, Chris M.; Alaqtash, Nabil; Chao, Hsien Wen; Chang, Tsun Hsu; Cheung, Chin Li "Barry"; Ahmad, A.; Qattan, I. A.; Sabirianov, Renat F.

In: Journal of Physics and Chemistry of Solids, Vol. 113, 01.02.2018, p. 82-85.

Research output: Contribution to journalArticle

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abstract = "Diisopropylammonium bromide (DIPAB) molecular ferroelectric crystals were synthesized and examined to exhibit a large electric polarization (∼23μC/cm2), a large dielectric constant in the α-phase. Although the PXRD pattern indicates that the α-DIPAB sample has an overall excellent crystallinity, our analysis of its FT-IR and Raman vibrational spectra suggests the presence of disorder in the synthesized crystals as indicated by the presence of broad features in the Raman spectrum. Using vdW+DF2 calculations, we identified the majority of vibrational modes in the experimental spectra and analyzed the ones due to Br-disorder. We found that the bromine (Br) deficiency strongly affects the electric properties of α-DIPAB. Particularly, the experimentally measured dielectric constant of α-DIPAB is large (∼20), whereas the DFT-based calculations of the ideal DIPAB give much smaller values (∼2-3). We find that Br-deficiency is responsible for large dielectric constant of the DIPAB crystal with calculated value of ∼15-20. Furthermore, we showed that the van der Waals forces have a slight effect on the structural parameters, only causing a small shift in the vibrational frequencies. The main vibrational features of the DIPAB crystal in the Raman spectrum were shown to be driven by covalent bonding in the DIPA molecules and hydrogen bonds between the molecules with Br.",
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T1 - Effect of bromine deficiency on the lattice dynamics and dielectric properties of alpha-phase diisopropylammonium bromide molecular crystals

AU - Alsaad, Ahmad

AU - Marin, Chris M.

AU - Alaqtash, Nabil

AU - Chao, Hsien Wen

AU - Chang, Tsun Hsu

AU - Cheung, Chin Li "Barry"

AU - Ahmad, A.

AU - Qattan, I. A.

AU - Sabirianov, Renat F

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N2 - Diisopropylammonium bromide (DIPAB) molecular ferroelectric crystals were synthesized and examined to exhibit a large electric polarization (∼23μC/cm2), a large dielectric constant in the α-phase. Although the PXRD pattern indicates that the α-DIPAB sample has an overall excellent crystallinity, our analysis of its FT-IR and Raman vibrational spectra suggests the presence of disorder in the synthesized crystals as indicated by the presence of broad features in the Raman spectrum. Using vdW+DF2 calculations, we identified the majority of vibrational modes in the experimental spectra and analyzed the ones due to Br-disorder. We found that the bromine (Br) deficiency strongly affects the electric properties of α-DIPAB. Particularly, the experimentally measured dielectric constant of α-DIPAB is large (∼20), whereas the DFT-based calculations of the ideal DIPAB give much smaller values (∼2-3). We find that Br-deficiency is responsible for large dielectric constant of the DIPAB crystal with calculated value of ∼15-20. Furthermore, we showed that the van der Waals forces have a slight effect on the structural parameters, only causing a small shift in the vibrational frequencies. The main vibrational features of the DIPAB crystal in the Raman spectrum were shown to be driven by covalent bonding in the DIPA molecules and hydrogen bonds between the molecules with Br.

AB - Diisopropylammonium bromide (DIPAB) molecular ferroelectric crystals were synthesized and examined to exhibit a large electric polarization (∼23μC/cm2), a large dielectric constant in the α-phase. Although the PXRD pattern indicates that the α-DIPAB sample has an overall excellent crystallinity, our analysis of its FT-IR and Raman vibrational spectra suggests the presence of disorder in the synthesized crystals as indicated by the presence of broad features in the Raman spectrum. Using vdW+DF2 calculations, we identified the majority of vibrational modes in the experimental spectra and analyzed the ones due to Br-disorder. We found that the bromine (Br) deficiency strongly affects the electric properties of α-DIPAB. Particularly, the experimentally measured dielectric constant of α-DIPAB is large (∼20), whereas the DFT-based calculations of the ideal DIPAB give much smaller values (∼2-3). We find that Br-deficiency is responsible for large dielectric constant of the DIPAB crystal with calculated value of ∼15-20. Furthermore, we showed that the van der Waals forces have a slight effect on the structural parameters, only causing a small shift in the vibrational frequencies. The main vibrational features of the DIPAB crystal in the Raman spectrum were shown to be driven by covalent bonding in the DIPA molecules and hydrogen bonds between the molecules with Br.

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