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A comparative multi‐reference configuration interaction study of the low‐lying states of two thione isomers of thiophenol
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2020-06-11 , DOI: 10.1002/qua.26263 Filipe Belarmino de Lima 1 , Gessenildo Pereira Rodrigues 2 , Juracy Regis Lucena Júnior 3 , Elizete Ventura 1 , Rui Fausto 4 , Igor Reva 4 , Silmar Andrade Monte 1
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2020-06-11 , DOI: 10.1002/qua.26263 Filipe Belarmino de Lima 1 , Gessenildo Pereira Rodrigues 2 , Juracy Regis Lucena Júnior 3 , Elizete Ventura 1 , Rui Fausto 4 , Igor Reva 4 , Silmar Andrade Monte 1
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Multi‐reference configuration interaction, MR‐CI (including extensivity corrections, named +Q), calculations were performed on the S0–S3 states of cyclohexa‐2,4‐diene‐1‐thione (thione 24 ) and cyclohexa‐2,5‐diene‐1‐thione (thione 25 ), which are thione isomers of thiophenol. Several types of uncontracted MR‐CIS and MR‐CISD wavefunctions were employed, comprising MR‐CI expansions as large as ~365 × 106 configuration state functions. The nature of the studied excited states was characterized. Vertical excitation energies (ΔE ) and oscillator strengths (f ) were computed. The most intense transitions (S0 → S2 for 24 and S0 → S3 for 25 ) did not change with the wavefunction, although a variation as large as ~1 eV was obtained for the S3 state of 24 , at the highest (MR‐CI+Q) level. On the other hand, ΔE changed at most by ~0.56 eV for 25 as the wavefunction changes, at the same level. The S1 state of both thiones was found to have nπ * character and is in the visible region. For 24 , S2 and S3 are ππ * and nπ * states, respectively, while for 25 the reverse order is obtained. S2 and S3 are in the range ~3.5 to 5.2 eV, again at the highest level. It is the first time that the excited states of the title molecules are studied. The computed results agree with the experimental onset of photoreactions of thiones 24 and 25 found by Reva et al (Phys. Chem. Chem. Phys. , 2015 , 17 , 4888).
中文翻译：
苯硫酚的两种硫酮异构体低价态的比较多参考构型相互作用研究
多参考配置相互作用MR-CI（包括扩展性校正，命名为+ Q）是根据环己2,4-二烯-1-硫酮（thione 24）和环己2-2的S 0 -S 3状态进行的计算，5-二烯-1-硫酮（thione 25），它们是硫酚的硫酮异构体。使用了几种未签约的MR-CIS和MR-CISD波函数，包括MR-CI扩展，最大约为365×10 6配置状态函数。研究了激发态的性质。计算了垂直激发能（ΔE）和振荡器强度（f）。最强烈的过渡（S 0 →S 2为24和S 0 →S 3为25）不与所述波函数改变，尽管对于S得到大至〜1电子伏特的变化3的状态24，在最高（MR-CI + Q）的水平。另一方面，随着波函数的变化，ΔE在25时最多变化〜0.56 eV 。在S 1两种硫酮的状态，发现有n个π *字符是在可见光区域。为24，S 2和S 3是ππ *和n π分别*状态，而对于在图25中，获得相反的顺序。S 2和S 3在〜3.5至5.2 eV的范围内，再次处于最高水平。这是第一次研究标题分子的激发态。所计算的结果与硫酮的光反应的实验开始24和25由雷瓦等（发现的PHY。化学式化学物理。，2015，17，4888）。
更新日期：2020-07-05
中文翻译：
苯硫酚的两种硫酮异构体低价态的比较多参考构型相互作用研究
多参考配置相互作用MR-CI（包括扩展性校正，命名为+ Q）是根据环己2,4-二烯-1-硫酮（thione 24）和环己2-2的S 0 -S 3状态进行的计算，5-二烯-1-硫酮（thione 25），它们是硫酚的硫酮异构体。使用了几种未签约的MR-CIS和MR-CISD波函数，包括MR-CI扩展，最大约为365×10 6配置状态函数。研究了激发态的性质。计算了垂直激发能（ΔE）和振荡器强度（f）。最强烈的过渡（S 0 →S 2为24和S 0 →S 3为25）不与所述波函数改变，尽管对于S得到大至〜1电子伏特的变化3的状态24，在最高（MR-CI + Q）的水平。另一方面，随着波函数的变化，ΔE在25时最多变化〜0.56 eV 。在S 1两种硫酮的状态，发现有n个π *字符是在可见光区域。为24，S 2和S 3是ππ *和n π分别*状态，而对于在图25中，获得相反的顺序。S 2和S 3在〜3.5至5.2 eV的范围内，再次处于最高水平。这是第一次研究标题分子的激发态。所计算的结果与硫酮的光反应的实验开始24和25由雷瓦等（发现的PHY。化学式化学物理。，2015，17，4888）。
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