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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electronic Excitation in a Saturated Chain:A MS-CASPT2 Treatment of the Anti Conformer of n-Tetrasilane
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Electronic Excitation in a Saturated Chain:A MS-CASPT2 Treatment of the Anti Conformer of n-Tetrasilane

机译：饱和链中的电子激发：正丁硅烷反构异构体的MS-CASPT2处理

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摘要

The singlet-singlet electronic spectrum of the anti conforemr of n-tertrasilane has been studied using multiconfigurational wave fuctions (CASSCF),second-order perturbation theory(CASPT2),and its multi-state extension ((MS-CASPT2),in conjunction with large ANO-type basis sets including Rydberg functions.The calculations include the 4S,4P,and 3d members of the Rydberg series converging on the first ionization.Mixing f valence and Rydberg states observedint he CASSCF wave functions is not fully rectified by single-reference CASPT2 method separates the valence and Rydberg states effectively.At the MS-CASPT2 level,six valence excited states have been found below the lowest Rydberg transition ,predicted at 7.40 eV.In terms of natural orbitals,they correspond to single electron promotions from the #delta#-symmetry HOMO to four #delta#* and two #pi#* valence orbitals.Vertical dipole-allowed valence transition energies (oscillator strengths)are computed at 6.33 eV(1.12),6.68 eV(0.01),and 6.96eV(0.15),for excitationto 1~1B_u,1~1A_u,and 2~1B_u states,respectively.Three vertical dipole-forbidden valence transitions are predicted to be interleaved among them at 6.55 eV(2~1A_g),6.87 eV(3~1A_g),and 7.10 eV(1~1B_g).The results are consistent with the available experimetnal data and are easily rationalized in terms of a simple Huckel model of #delta# delocalization.
机译：使用多构型波函数（CASSCF），二阶扰动理论（CASPT2）及其多态扩展（（MS-CASPT2）包括Rydberg函数在内的大型ANO型基集。计算包括Rydberg系列的4S，4P和3d成员在第一次电离时收敛。观察到混合价和Rydberg状态，因为CASSCF波函数没有被单参考完全校正。 CASPT2方法有效地分离了价态和Rydberg态。在MS-CASPT2水平上，在最低Rydberg跃迁以下（预测为7.40 eV）发现了六个价态激发态。就自然轨道而言，它们对应于＃到四个＃delta＃*和两个＃pi＃*价轨道的delta＃对称HOMO。在6.33 eV（1.12），6.68 eV（0.01）和6.96e处计算了垂直偶极子允许的价态跃迁能（振荡器强度）。 V（0.15），分别激发到1〜1B_u，1〜1A_u和2〜1B_u状态。三个垂直的偶极子禁态价态跃迁在6.55 eV（2〜1A_g），6.87 eV（3 〜1A_g）和7.10 eV（1〜1B_g）。结果与可用的实验数据一致，并且可以通过简单的＃delta＃离域Huckel模型合理化。

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