A comprehensive analysis of the structural, conformational, and spectroscopic properties in the gas phase has been performed for five prototypical steroid hormones, namely, androsterone, testosterone, estrone, β-estradiol, and estriol. The revDSD-PBEP86 double-hybrid functional in conjunction with the D3BJ empirical dispersion and a suitable triple-ζ basis set provides accurate conformational energies and equilibrium molecular structures, with the latter being further improved by proper account of core–valence correlation. Average deviations within 0.1% between computed and experimental ground state rotational constants are reached when adding to those equilibrium values vibrational corrections obtained at the cost of standard harmonic frequencies thanks to the use of a new computational tool. Together with the intrinsic interest of the studied hormones, the accuracy of the results obtained at DFT cost for molecules containing about 50 atoms paves the way toward the accurate investigations of other flexible bricks of life.

中文翻译：

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以 DFT 成本计算类固醇激素的精确结构和旋转常数：雄酮、睾酮、雌酮、β-雌二醇和雌三醇

对五种典型类固醇激素（即雄酮、睾酮、雌酮、β-雌二醇和雌三醇）的气相结构、构象和光谱特性进行了全面分析。 revDSD-PBEP86 双杂化泛函与 D3BJ 经验色散和合适的三重 ze 基组相结合，提供了准确的构象能量和平衡分子结构，后者通过正确考虑核价相关性而得到进一步改进。由于使用了新的计算工具，加上以标准谐波频率为代价获得的振动校正平衡值，计算出的基态旋转常数与实验基态旋转常数之间的平均偏差在 0.1% 以内。加上所研究的激素的内在兴趣，以 DFT 成本获得的包含约 50 个原子的分子的结果的准确性，为准确研究其他灵活的生命砖铺平了道路。