Ab Initio Optimized All-Atom Force Field for Vapor–Liquid Equilibria Simulation of Trifluoromethanesulfonyl Fluoride

IF 2 3区 化学 Q3 CHEMISTRY, PHYSICAL
Wei Liu, Yumei Song, Mi Zhang, Jiageng Xiong, Hua Hou, Baoshan Wang
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Abstract

Trifluoromethanesulfonyl fluoride (CF3SO2F) has attracted great interest as a promising replacement gas for sulfur hexafluoride in view of its excellent dielectric performance. The electronic structures of CF3SO2F and a total of seven dimeric complexes have been characterized theoretically using the M06-2X density functionals with the basis set up to 5-ζ (aug-cc-pV5Z + d) and Grimme's D3 dispersion corrections, the coupled-cluster with single, double, and non-iterative triple energies extrapolated to the complete basis set limit, and the symmetry-adapted perturbation theory (SAPT). The dimeric binding energies are in the range of 1–3 kcal mol−1, depending strongly on the relative orientations of the monomers. The dominant dimerization occurs via the concerted interactions between CF3 and SO2 groups. A classical all-atom force field has been developed successfully for CF3SO2F on the basis of the SAPT-calculated decomposition asymptotes of the dimeric complexes. The vapor–liquid coexistence equilibria have been predicted using the hybrid Gibbs ensemble Monte Carlo algorithm. Theoretical vapor pressures and boiling point of CF3SO2F are in good agreement with the latest experimental data. In comparison with perfluoronitrile, CF3SO2F is superior in terms of liquefaction temperature but inferior in both viscosity and thermal conductivity. The present work sheds new light on the use of CF3SO2F as a promising alternative to dielectric and refrigerant fluids.

Abstract Image

从头算优化三氟甲烷磺酰氟汽液平衡模拟的全原子力场
三氟甲烷磺酰氟(CF3SO2F)由于其优异的介电性能,作为一种有前途的六氟化硫替代气体引起了人们的极大兴趣。利用基集为5-ζ (aug-cc-pV5Z + d)的M06-2X密度泛函和grime 's D3色散修正,单、双、非迭代三重能的耦合簇外推至完全基集极限,以及对称自适应微扰理论(SAPT),对CF3SO2F和共7种二聚物的电子结构进行了理论表征。二聚体的结合能在1 - 3千卡摩尔−1之间,这很大程度上取决于单体的相对取向。主要二聚化是通过CF3和SO2基团之间的协同相互作用发生的。基于sapt计算的二聚体配合物的分解渐近线,成功地建立了CF3SO2F的经典全原子力场。利用杂化Gibbs系综蒙特卡洛算法预测了气液共存平衡态。CF3SO2F的理论蒸汽压和沸点与最新实验数据吻合较好。与全氟腈相比,CF3SO2F在液化温度上优于CF3SO2F,但在粘度和导热性上均优于CF3SO2F。目前的工作为使用CF3SO2F作为电介质和制冷剂流体的有前途的替代品提供了新的思路。
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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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