Spectral Characteristic of Phosgene in External Electric Field
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Keywords

Density-functional theory
Phosgene
Spectrum characteristic
External electric field
Molecular dynamics

DOI

10.26689/jera.v6i2.3744

Abstract

Phosgene is highly toxic, and it plays a role in the depletion of the ozone layer. The ground state geometric structure and spectral characteristic of phosgene in various external electric fields were calculated via the density-functional theory (DFT) and time-dependent density-functional theory (TDDFT) with the B3LYP/6-31+G(d) basis set. With external electric field, the structure of phosgene changed significantly. With increasing electric field, the bond lengths of 1C-3Cl and 1C-4Cl increased; the total energy and energy gap initially increased and then decreased, whereas the dipole moment initially decreased and then increased. Most of the IR vibrational frequencies were redshifted. The wavelength of the singlet excited state increased, reflecting a red shift, and the oscillator strengths of most transitions belonged to forbidden transitions. These results are of great significance for studying the dissociation of phosgene in external electric field.

References

Molina MJ, Rowland FS, 1974, Stratospheric Sink for Chlorofluoromethanes: Chlorine Atomc-Atalysed Destruction of Ozone. Nature, 249(5460): 810-812.

Zhang ZM, 1999, Who Discovered the Ozone Hole?. Friends of Chemical Industry, 39(02): 45.

Chen HY, Lien CY, Lin WY, 2009, UV absorption Cross Sections of Cloocl Are Consistent with Ozone Degradation Models. Science, 324(5928): 781.

Lan YC, Wang H, Wu LX, et al., 2012, Electroreduction of Dibromobenzenes on Silver Electrode in the Presence of CO2. Journal of Electroanalytical Chemistry, 664(15): 33-38.

Wu HY, 2006, Analysis of Halon Substitute Agent Environment Affection and Study on Extinguishing System of Halon Substitutes, Tianjin University, Tianjin.

Li XH, Liu YZ, Chen YY, et al., 2018, Investigation on Molecular Properties of Freon 13 in External Electric Field. Journal of Molecular Science, 34(2): 139-143.

Xu HP, Ying YH, 2016, The molecular Structure and Properties of Agcl Under External Electric Field. Journal of Atomic and Molecular Physics, 33(1): 1-7.

Zhou ZY, Liu YZ, Li J, et al., 2017, Influence of External Electric Field on the Molecular Structure and Electronic Spectrum of Formaldehyde Molecule. Journal of Molecular Science, 33(3): 217-224.

Wang JP, Zhai DD, Ma P, et al., 2020, Theoretical Insight into the Effects of External Electric Field on Cocrystal HMX/DMI. Journal of Propellants and Explosives, 43(2): 133-138.

Vossnacke P, Wust A, Keilhack T, et al., 2021, Novel Synthetic Pathway for the Production of Phosgene. Science Advances, 7(40): 5186.

Li J, Liu YZ, Yin WY, et al., 2017, Spectra and Dissociation Properties of Freon 31 Under Electric Field. Spectroscopy Letters, 50(10): 572-578.

Hobson ST, Casillas RP, Richieri RA, et al., 2019, Development of an Acute, Short-Term Exposure Model for Phosgene. Toxicology Mechanisms and Methods, 29(8): 604-615.

Olivera DS, Hoard-Fruchey H, Sciuto AM, 2016, Evaluation of an in Vitro Screening Model to Assess Phosgene Inhalation Injury. Toxicology Methods, 27(1): 45-51.

Hobson ST, Richieri RA, Parseghian MH, 2021, Phosgene: Toxicology, Animal Models, and Medical Countermeasures. Toxicology Mechanisms and Methods, 31(4): 293-307.

Lu QY, Huang SY, Meng XY, et al., 2021, Mechanism of Phosgene-Induced Acute Lung Injury and Treatment Strategy. International Journal of Molecular Sciences, 22(20): 10933.

Pitschmann V, Matejovsky L, Zeman J, et al., 2020, Second-Generation Phosgene and Diphosgene Detection Tube. Chemosensors, 8(4): 107.

Khan S, Sajid H, Ayub K, et al., 2020, High Sensitivity of Graphdiyne Nanoflake toward Detection of Phosgene, Thiophosgene and Phosogenoxime; A First-Principles Study. Journal of Molecular Graphics and Modelling, 100(prepublish): 107658.

Wang SL, Zhong L, Song QH, 2018, Sensitive and Selective Detection of Phosgene, Diphosgene, and Triphosgene by a 3,4-Diaminonaphthalimide in Solutions and the Gas Phase. Chemistry (Weinheim an der Bergstrasse, Germany), 24(21): 5652-5658.

Carlos LHJ, Baptiste S, Laurent V, et al., 2018, Thermal Decomposition of Phosgene and Diphosgene. The Journal of Physical Chemistry A, 122(1): 249-257.

Liu YZ, Li XH, Wang JF, et al., 2017, Study on Dissociation Properties and Spectra of Halon 1301 in External Electric Field. Spectroscopy and Spectral Analysis, 37(03): 679-684.

Zhang XYZ, Liu YZ, Ma XY, 2018, Dissociation and Physical Properties of Methyl Iodide in External Electric Field. Journal of University of Chinese Academy of Sciences, 35(06): 839-844.

Wu YG, Liu JX, Liu HL, et al., 2019, Spectrum and Dissociation Properties of Fluoro Trichloro Methane Molecule in Radiational Field. Acta Physical Sonica, 68(06): 64-72.

Frish MJ, Trucks GW, Schlegel HB, et al., 2010, Gaussian 09, Revision C. 01., Gaussian, Inc., Wallingford.

Shimanouchi T, 1977, Tables of Molecular Vibrational Frequencies. Consolidated. Volume II. Journal of Physical and Chemical Reference Data, 6(3): 103.

Zhu ZH, 1991, Atomic and Molecular Reaction Statics, Science Press, Beijing.

Cardona CM, Li W, Kaifer AE, et al., 2011, Electrochemical Considerations for determining Absolute Frontier Orbital Energy Levels of Conjugated Polymers for Solar Cell Applications. Advanced Materials, 23(20): 2367-2371.

Li J, Liu YZ, Cheng QY, et al., 2017, Study on the Physical Characteristics of Halon-1211 Under the Electrical Fields. Journal of Atomic and Molecular Physics, 34(6): 1017-1024.

Yin YH, Wang L, 2017, Structure and Properties of AgBr Molecule Under External Electric Field. Journal of Atomic and Molecular Physics, 34(1): 9-15.