Nonlinear optical property calculations of polyynes with long-range corrected hybrid exchange-correlation functionals.
Nonlinear optical property calculations of polyynes with long-range corrected hybrid exchange-correlation functionals.
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使用长程校正混合交换相关泛函计算多炔的非线性光学性质。
DOI：
10.1063/1.2936830
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发表时间：
2008
期刊：
影响因子：
--
通讯作者：
K. Hirao
中科院分区：
文献类型：
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作者：
Jong;M. Watson;H. Sekino;K. Hirao
利用长程校正（LC）密度泛函理论（DFT）、LC-DFT与短程高斯衰减（LCgau）以及高质量波函数方法，对聚炔[H-(c[三键]c) (n)-H, n = 1-8]的极化率（alpha）、二次超极化率（gamma）和γ标度因子(c)进行了评价。我们证明了LC-和LCgau-DFT计算得到的c值与CCSD(T)计算得到的c值一致。此外，我们获得的聚烯c值被认为小于先前计算的多烯γ值的c值[Sekino et al.， J. Chem.]。物理学报，126,014107(2007)]。我们将我们的结果与实验得到的结果进行比较[Shepkov et al.， J. Chem]。物理学报，2004,18(4)。[i-Pr(3)Si-(C[三键]C)(n)- sii - pr(3)]，多炔的C值大于多烯。我们用i-Pr(3)Si-(C[三键]C)(n)-Si - pr (3) （n = 4,5,6和8）计算的α和γ表明，i-Pr(3)Si-可能参与π分子轨道离域，从而意外地影响C值。我们也证实了分子几何在这些非线性光学计算中的重要性。我们发现LC-和LCgau-DFT很好地再现了实验几何形状和键长交替（BLA），而MP2优化的几何形状的BLA太短，无法用于精确的α和γ计算。
Polarizabilities (alpha), second-hyperpolarizabilities (gamma), and the gamma scaling factors (c) of polyynes [H-(C[triple bond]C)(n)-H, n = 1-8] were evaluated using the long-range corrected (LC) density functional theory (DFT) and LC-DFT with a short-range Gaussian attenuation (LCgau), as well as high quality wavefunction methods. We show that the c values obtained from LC- and LCgau-DFT are consistent with those from CCSD(T) calculations. Furthermore, the polyyne c values we obtained are seen to be smaller than the c values derived from previously calculated polyene gamma values [Sekino et al., J. Chem. Phys. 126, 014107 (2007)] in all the methods we consider. We compare our results with those obtained experimentally [Shepkov et al., J. Chem. Phys. 120, 6807 (2004).] from end-capped polyynes [i-Pr(3)Si-(C[triple bond]C)(n)-Sii-Pr(3)], which show larger c values for polyynes than polyenes. Our alpha and gamma calculations with i-Pr(3)Si-(C[triple bond]C)(n)-Sii-Pr(3) (n = 4, 5, 6, and 8) show that i-Pr(3)Si- may participate in pi molecular orbital delocalization, which can unexpectedly affect the c value. We also confirm the importance of molecular geometry in these nonlinear optical calculations. We find that while LC- and LCgau-DFT excellently reproduce experimental geometries and bond length alternation (BLA), MP2 optimized geometries have a BLA that is too short to be used for accurate alpha and gamma calculations.
DOI：
10.1063/1.2721532
发表时间：
2007-04
期刊：
The Journal of chemical physics
影响因子：
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作者：
Jong-Won Song;Tsuyoshi Hirosawa;T. Tsuneda;K. Hirao
通讯作者：
Jong-Won Song;Tsuyoshi Hirosawa;T. Tsuneda;K. Hirao
影响因子：
4.4
作者：
Tawada, Y;Tsuneda, T;Hirao, K
通讯作者：
Hirao, K
包括短程高斯衰减的长程校正混合交换相关函数的系统优化（LCgau-B97）
DOI：
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发表时间：
2009
期刊：
影响因子：
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作者：
Jong-Won Song;Daoling Peng;Kimihiko Hirao
通讯作者：
Kimihiko Hirao