Analysis of UV and vibrational spectra (FT-IR and FT-Raman) of hexachlorocyclotriphosphazene based on normal coordinate analysis, MP2 and DFT calculations

Wajdi M. Zoghaib, John Husband, Usama A. Soliman, Ibrahim A. Shaaban, Tarek A. Mohamed

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Abstract

The Raman (1400-100 cm-1) and infrared (4000-400 cm -1) of solid hexachlorocyclotriphosphazene, P3N 3Cl6 (HCCTP) were recorded. The conformational energies were calculated using MP2 and DFT (B3LYP and B3PW91) methods utilizing a variety of basis sets up to 6-311+G(d). On the basis of D3h symmetry, the simulated vibrational spectra of P3N3Cl6 from MP2 and DFT methods were in excellent agreement with those obtained experimentally. Additionally, Frontier Molecular Orbitals and electronic transitions were predicted using steady state and time dependent DFT(B3LYP)/PCM calculations respectively, each employing the 6-311+G(d,p) optimized structural parameters. The predicted wavelengths were in excellent agreement with experimental values when CH2Cl2 was used as solvent. The 14N and 31P chemical shifts were predicted with B3LYP/6-311+G(2d,p) calculations using the GIAO technique with solvent effect modeled using the PCM method. The computed structural parameters of the planar P3N3Cl6 (D3h) agree well with experimental values from both X-ray and electron diffraction data with slight distortions observed due to lattice defects in the solid phase. The experimental/computational results favor a slightly distorted D3h symmetry for the title compound in the gas and solid phases and in solution (τPNPN and τNPNP ranged from 0.018° to 0.90°). Aided by normal coordinate analysis, and the simulated vibrational spectra utilizing MP2, B3LYP and B3PW91 methods at 6-31G(d) basis set, revised and complete vibrational assignments for all fundamentals are provided herein.

Original languageEnglish
Pages (from-to)446-455
Number of pages10
JournalSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Volume105
DOIs
Publication statusPublished - Mar 15 2013

Fingerprint

Vibrational spectra
Discrete Fourier transforms
vibrational spectra
solid phases
Pulse code modulation
molecular electronics
symmetry
chemical equilibrium
Molecular electronics
molecular orbitals
electron diffraction
Crystal defects
Chemical shift
Molecular orbitals
vapor phases
Electron diffraction
defects
Gases
diffraction
wavelengths

Keywords

  • Hexachlorocyclotriphosphazene (HCCTP)
  • Normal coordinate analysis and quantum mechanical calculations
  • Vibrational assignments

ASJC Scopus subject areas

  • Instrumentation
  • Atomic and Molecular Physics, and Optics
  • Analytical Chemistry
  • Spectroscopy

Cite this

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title = "Analysis of UV and vibrational spectra (FT-IR and FT-Raman) of hexachlorocyclotriphosphazene based on normal coordinate analysis, MP2 and DFT calculations",
abstract = "The Raman (1400-100 cm-1) and infrared (4000-400 cm -1) of solid hexachlorocyclotriphosphazene, P3N 3Cl6 (HCCTP) were recorded. The conformational energies were calculated using MP2 and DFT (B3LYP and B3PW91) methods utilizing a variety of basis sets up to 6-311+G(d). On the basis of D3h symmetry, the simulated vibrational spectra of P3N3Cl6 from MP2 and DFT methods were in excellent agreement with those obtained experimentally. Additionally, Frontier Molecular Orbitals and electronic transitions were predicted using steady state and time dependent DFT(B3LYP)/PCM calculations respectively, each employing the 6-311+G(d,p) optimized structural parameters. The predicted wavelengths were in excellent agreement with experimental values when CH2Cl2 was used as solvent. The 14N and 31P chemical shifts were predicted with B3LYP/6-311+G(2d,p) calculations using the GIAO technique with solvent effect modeled using the PCM method. The computed structural parameters of the planar P3N3Cl6 (D3h) agree well with experimental values from both X-ray and electron diffraction data with slight distortions observed due to lattice defects in the solid phase. The experimental/computational results favor a slightly distorted D3h symmetry for the title compound in the gas and solid phases and in solution (τPNPN and τNPNP ranged from 0.018° to 0.90°). Aided by normal coordinate analysis, and the simulated vibrational spectra utilizing MP2, B3LYP and B3PW91 methods at 6-31G(d) basis set, revised and complete vibrational assignments for all fundamentals are provided herein.",
keywords = "Hexachlorocyclotriphosphazene (HCCTP), Normal coordinate analysis and quantum mechanical calculations, Vibrational assignments",
author = "Zoghaib, {Wajdi M.} and John Husband and Soliman, {Usama A.} and Shaaban, {Ibrahim A.} and Mohamed, {Tarek A.}",
year = "2013",
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journal = "Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy",
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T1 - Analysis of UV and vibrational spectra (FT-IR and FT-Raman) of hexachlorocyclotriphosphazene based on normal coordinate analysis, MP2 and DFT calculations

AU - Zoghaib, Wajdi M.

AU - Husband, John

AU - Soliman, Usama A.

AU - Shaaban, Ibrahim A.

AU - Mohamed, Tarek A.

PY - 2013/3/15

Y1 - 2013/3/15

N2 - The Raman (1400-100 cm-1) and infrared (4000-400 cm -1) of solid hexachlorocyclotriphosphazene, P3N 3Cl6 (HCCTP) were recorded. The conformational energies were calculated using MP2 and DFT (B3LYP and B3PW91) methods utilizing a variety of basis sets up to 6-311+G(d). On the basis of D3h symmetry, the simulated vibrational spectra of P3N3Cl6 from MP2 and DFT methods were in excellent agreement with those obtained experimentally. Additionally, Frontier Molecular Orbitals and electronic transitions were predicted using steady state and time dependent DFT(B3LYP)/PCM calculations respectively, each employing the 6-311+G(d,p) optimized structural parameters. The predicted wavelengths were in excellent agreement with experimental values when CH2Cl2 was used as solvent. The 14N and 31P chemical shifts were predicted with B3LYP/6-311+G(2d,p) calculations using the GIAO technique with solvent effect modeled using the PCM method. The computed structural parameters of the planar P3N3Cl6 (D3h) agree well with experimental values from both X-ray and electron diffraction data with slight distortions observed due to lattice defects in the solid phase. The experimental/computational results favor a slightly distorted D3h symmetry for the title compound in the gas and solid phases and in solution (τPNPN and τNPNP ranged from 0.018° to 0.90°). Aided by normal coordinate analysis, and the simulated vibrational spectra utilizing MP2, B3LYP and B3PW91 methods at 6-31G(d) basis set, revised and complete vibrational assignments for all fundamentals are provided herein.

AB - The Raman (1400-100 cm-1) and infrared (4000-400 cm -1) of solid hexachlorocyclotriphosphazene, P3N 3Cl6 (HCCTP) were recorded. The conformational energies were calculated using MP2 and DFT (B3LYP and B3PW91) methods utilizing a variety of basis sets up to 6-311+G(d). On the basis of D3h symmetry, the simulated vibrational spectra of P3N3Cl6 from MP2 and DFT methods were in excellent agreement with those obtained experimentally. Additionally, Frontier Molecular Orbitals and electronic transitions were predicted using steady state and time dependent DFT(B3LYP)/PCM calculations respectively, each employing the 6-311+G(d,p) optimized structural parameters. The predicted wavelengths were in excellent agreement with experimental values when CH2Cl2 was used as solvent. The 14N and 31P chemical shifts were predicted with B3LYP/6-311+G(2d,p) calculations using the GIAO technique with solvent effect modeled using the PCM method. The computed structural parameters of the planar P3N3Cl6 (D3h) agree well with experimental values from both X-ray and electron diffraction data with slight distortions observed due to lattice defects in the solid phase. The experimental/computational results favor a slightly distorted D3h symmetry for the title compound in the gas and solid phases and in solution (τPNPN and τNPNP ranged from 0.018° to 0.90°). Aided by normal coordinate analysis, and the simulated vibrational spectra utilizing MP2, B3LYP and B3PW91 methods at 6-31G(d) basis set, revised and complete vibrational assignments for all fundamentals are provided herein.

KW - Hexachlorocyclotriphosphazene (HCCTP)

KW - Normal coordinate analysis and quantum mechanical calculations

KW - Vibrational assignments

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U2 - 10.1016/j.saa.2012.11.071

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M3 - Article

VL - 105

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EP - 455

JO - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy

JF - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy

SN - 1386-1425

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