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DOI	10.1016/j.atmosenv.2020.117363
	Approach to evaluate the gas/aerosol partition coefficient of organic volatile compounds using DFT methods associated with polarizable continuum models
	de Castilho L.L.; dos Santos F.E.B.; Baptista L.
发表日期	2020
ISSN	1352-2310
卷号	224
英文摘要	Gas/aerosol partition coefficients are important to the development of air quality models that include the physical chemistry of atmospheric aerosols because they are related to the solubility of gases in water. This paper presents an approach to calculate these coefficients using DFT methods associated with polarizable continuum models to include the solvent effect. The methodology was tested by comparing DFT-calculated Henry's law constants of 27 terpenes with experimental data available in the literature. Furthermore, Henry's law constants of the d-limonene and Δ3-carene oxidation products were evaluated. A correction to the ideal solution behavior was performed by evaluating the activity coefficient of each solute considering the aerosol's physical-chemical properties (size, pH and ionic strength), followed by the calculation of the gas/aerosol partition coefficient. The mean average deviations of the PBE1PBE and M06–2X functionals, excluding oxidized terpenes and considering the SMD model (Solvation Model Based on Solute Electron Density), were 2.26 × 10−4 m³ mol Pa−1 and 2.23 × 10−4 m³ mol Pa−1, respectively. As a general trend, the presence of inorganic compounds in aerosols lowers the solubility of oxidation products, which makes the transfer of organic species from the gas phase to the aerosol phase difficult. The proposed approach is simpler than methods involving explicit solvation models and does not require ensemble averages to be applied. The method returns reliable Henry's law constants of terpenes; however, experimental measurements are necessary to validate the constants computed for terpene oxidation products. © 2020 Elsevier Ltd
关键词	Density functional methods Gas/aerosol partition coefficient Henry's law constant Oxidation products SMD model Terpenes
语种	英语
scopus关键词	Air quality; Atmospheric aerosols; Atmospheric chemistry; Continuum mechanics; Density functional theory; Gases; Inorganic compounds; Ionic strength; Oxidation; pH; Physical chemistry; Solubility; Solvation; Solvents; Terpenes; Volatile organic compounds; Air quality models; Density-functional methods; Ensemble averages; Henry's Law constant; Oxidation products; Partition coefficient; Physical chemical property; Polarizable continuum model; Density of gases; terpene; volatile organic compound; activity coefficient; aerosol composition; air quality; oxidation; physicochemical property; polarization; solubility; solute transport; terpene; volatile organic compound; aerosol; Article; calculation; chemical structure; density functional theory; gas; ionic strength; mathematical computing; methodology; partition coefficient; pH; physical chemistry; priority journal; solvent effect; trend study
来源期刊	ATMOSPHERIC ENVIRONMENT
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/249294
作者单位	Universidade do Estado do Rio de Janeiro, Faculdade de Tecnologia, Departamento de Química e Ambiental, Rodovia Presidente Dutra Km 298, Resende, RJ, Brazil
推荐引用方式 GB/T 7714	de Castilho L.L.,dos Santos F.E.B.,Baptista L.. Approach to evaluate the gas/aerosol partition coefficient of organic volatile compounds using DFT methods associated with polarizable continuum models[J],2020,224.
APA	de Castilho L.L.,dos Santos F.E.B.,&Baptista L..(2020).Approach to evaluate the gas/aerosol partition coefficient of organic volatile compounds using DFT methods associated with polarizable continuum models.ATMOSPHERIC ENVIRONMENT,224.
MLA	de Castilho L.L.,et al."Approach to evaluate the gas/aerosol partition coefficient of organic volatile compounds using DFT methods associated with polarizable continuum models".ATMOSPHERIC ENVIRONMENT 224(2020).