Department of Chemistry, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
J Phys Chem B. 2013 Jan 10;117(1):273-88. doi: 10.1021/jp307328x. Epub 2012 Dec 21.
The explicit-hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to various substituted benzenes through the parametrization of the exocyclic groups -F, -Cl, -Br, -C≡N, and -OH and to polycyclic aromatic hydrocarbons through the parametrization of the aromatic linker carbon atom for multiple rings. The linker carbon together with the TraPPE-EH parameters for aromatic heterocycles constitutes a force field for fused-ring heterocycles. Configurational-bias Monte Carlo simulations in the Gibbs ensemble were carried out to compute vapor-liquid coexistence curves for fluorobenzene; chlorobenzene; bromobenzene; di-, tri-, and hexachlorobenzene isomers; 2-chlorofuran; 2-chlorothiophene; benzonitrile; phenol; dihydroxybenzene isomers; 1,4-benzoquinone; naphthalene; naphthalene-2-carbonitrile; naphthalen-2-ol; quinoline; benzo[b]thiophene; benzo[c]thiophene; benzoxazole; benzisoxazole; benzimidazole; benzothiazole; indole; isoindole; indazole; purine; anthracene; and phenanthrene. The agreement with the limited experimental data is very satisfactory, with saturated liquid densities and vapor pressures reproduced to within 1.5% and 15%, respectively. The mean unsigned percentage errors in the normal boiling points, critical temperatures, and critical densities are 0.9%, 1.2%, and 1.4%, respectively. Additional simulations were carried out for binary systems of benzene/benzonitrile, benzene/phenol, and naphthalene/methanol to illustrate the transferability of the developed potentials to binary systems containing compounds of different polarity and hydrogen-bonding ability. A detailed analysis of the liquid-phase structures is provided for selected neat systems and binary mixtures.
可转移相平衡势能（TraPPE-EH）显氢版本通过对 -F、-Cl、-Br、-C≡N 和 -OH 等外环己基以及多环芳烃的芳香键碳原子的参数化，扩展到各种取代苯。键碳原子与 TraPPE-EH 芳香杂环参数一起构成了稠环杂环的力场。在吉布斯系综中进行了构象偏差蒙特卡罗模拟，以计算氟苯；氯苯；溴苯；二氯、三氯和六氯苯异构体；2-氯呋喃；2-氯噻吩；苯甲腈；苯酚；二羟基苯异构体；1,4-苯醌；萘；萘-2-腈；萘-2-醇；喹啉；苯并噻吩；苯并噻吩；苯并恶唑；苯并异恶唑；苯并咪唑；苯并噻唑；吲哚；异吲哚；吲唑；嘌呤；蒽和菲的汽液共存曲线。与有限的实验数据非常吻合，饱和液体密度和蒸汽压的再现误差分别在 1.5%和 15%以内。正常沸点、临界温度和临界密度的平均无符号百分比误差分别为 0.9%、1.2%和 1.4%。还对苯/苯甲腈、苯/苯酚和萘/甲醇的二元体系进行了额外的模拟，以说明开发的势能对含有不同极性和氢键能力的化合物的二元体系的可转移性。为选定的纯体系和二元混合物提供了详细的液相结构分析。
