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RESEARCH PRODUCT
Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species
Erkki KolehmainenHeikki M. TuononenJ. Mikko RautiainenHannu T. Vuorisubject
organophosphorus speciesEmpirical dataphosphine oxideslämpökemiaThermodynamics010402 general chemistry01 natural sciencesHeat capacitychemistry.chemical_compoundAdditive function0103 physical sciencesThermochemistrythermochemistryta116AlkylQuantum chemicalchemistry.chemical_classification010304 chemical physicsGeneral Chemistrylaskennallinen kemiaStandard enthalpy of formation0104 chemical sciencesComputational MathematicsphosphineschemistryPhosphinedescription
Composite quantum chemical methods W1X-1 and CBS-QB3 are used to calculate the gas phase standard enthalpy of formation, entropy, and heat capacity of 38 phosphines and phosphine oxides for which reliable experimental thermochemical information is limited or simply nonexistent. For alkyl phosphines and phosphine oxides, the W1X-1, and CBS-QB3 results are mutually consistent and in excellent agreement with available G3X values and empirical data. In the case of aryl-substituted species, different computational methods show more variation, with G3X enthalpies being furthest from experimental values. The calculated thermochemical data are subsequently used to determine Benson group additivity contributions for 24 Benson groups and group pairs involving phosphorus, thereby allowing fast and accurate estimations of thermochemical data of many organophosphorus compounds of any complexity. Such data are indispensable, for example, in chemical process design or estimating potential hazards of new chemical compounds. © 2018 Wiley Periodicals, Inc.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2018-12-21 | Journal of Computational Chemistry |