Conformations of 2,4-Diphenylpentane: A Quantum Chemistry and Gas-Phase Molecular Dynamics Simulation Study
Conformations of 2,4-Diphenylpentane: A Quantum Chemistry and Gas-Phase Molecular Dynamics Simulation Study
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2,4-二苯基戊烷的构象：量子化学和气相分子动力学模拟研究
DOI：
10.1021/jp9808936
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发表时间：
1998
影响因子：
2.9
通讯作者：
Aaron Bernarbo
中科院分区：
文献类型：
--
作者：
Grant D. Smith;Chakravarthy Ayyagari;R. Jaffe;M. Pekny;Aaron Bernarbo
我们报告的相对构象能量和旋转能垒的内消旋和外消旋的2，4-二苯基戊烷（DPP）的从头计算的电子结构计算。它被发现，苯环之间的色散相互作用强烈影响的构象几何，有必要包括电子相关的几何优化和能量计算。此外，通过从优化的DPP几何结构中提取苯环并计算所得苯二聚体构型的基组叠加误差来估计基组叠加对苯基-苯基相互作用的贡献是显着的。对原子分子力学力场进行参数化，以重现从头算获得的DPP中构象能和转动能垒的最佳值。构象能量等高线图的DPP对映体，并讨论了其显着特点。气相分子动力学模拟
We report on the relative conformer energies and rotational energy barriers for meso and racemic 2,4-diphenylpentane (DPP) from ab initio electronic structure calculations. It is found that dispersion interactions between phenyl rings strongly influence the conformational geometries, necessitating the inclusion of electron correlation in both geometry optimizations and energy calculations. Furthermore, basis set superposition contributions to the phenyl−phenyl interactions, estimated by extracting the phenyl rings from the optimized DPP geometries and computing the basis set superposition error for the resulting benzene dimer configurations, are significant. An atomistic molecular mechanics force field is parametrized to reproduce our best values for the conformational energies and rotational energy barriers in DPP obtained from ab initio calculations. Conformational energy contour maps are presented for the DPP enantiomers, and their salient features are discussed. Gas-phase molecular dynamics simulation...