• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers: Diradical character and spin multiplicity dependences
【24h】

Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers: Diradical character and spin multiplicity dependences

机译：涉及乙炔和亚乙烯基接头的菲基自由基系统第二超极化性的理论研究：双自由基特征和自旋多重性依赖性

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

We have investigated the static second hyperpolarizabilities (gamma) of the singlet diradical systems with intermediate diradical character involving phenalenyl radicals connected by acetylene and vinylene pi-conjugated linkers, 1 and 2, using the hybrid density functional theory. For comparison, we have also examined the gamma values of the closed-shell and pure diradical systems with almost the same molecular size as 1 and 2. In agreement with our previous prediction of the diradical character dependence of gamma, it turns out that the gamma values of 1 and 2 are significantly enhanced compared to those of the closed-shell and pure diradical systems. In the present case, distinct differences in gamma values are not observed between the two pi-conjugated linkers, though the diradical character is found to depend on the kind of linker. Furthermore, we have investigated the spin multiplicity effect on gamma. Changing from the singlet to the triplet state, the gamma values of the systems with intermediate diradical character in the singlet state are quite reduced, though those of the pure diradical systems are hardly changed. Such spin multiplicity dependence of gamma is understood by considering the difference of diradical character between their singlet states together with the Pauli principle. The present results provide a possibility of a novel control scheme of gamma for phenalenyl radical systems involving pi-conjugated linkers by adjusting the diradical character through the change of the linked position of pi-conjugated linkers and the spin multiplicity.
机译：我们使用混合密度泛函理论研究了具有中间双自由基特性的单线双自由基体系的静态第二超极化率（γ），该中间双自由基特性涉及通过乙炔和亚乙烯基π-共轭连接体1、2连接的苯二甲酰基。为了进行比较，我们还研究了分子大小与1和2几乎相同的闭壳和纯双自由基体系的γ值。与我们先前对γ的双自由基性相关性的预测相一致，事实证明，该γ与闭壳和纯双自由基体系相比，1和2的值显着提高。在当前情况下，虽然发现双自由基特性取决于接头的种类，但是在两个π-共轭的接头之间未观察到γ值的明显差异。此外，我们研究了自旋多重性对伽玛的影响。从单重态转变为三重态，虽然单双价体系的基本伽马值几乎不变，但在单重态时具有中等双自由基特征的系统的伽马值已大大降低。通过考虑其单重态与Pauli原理之间的双自由基特性的差异，可以理解这种自旋多重性。本结果为通过改变π-共轭连接基的连接位置和自旋多重性来调节双自由基特性，为涉及π-共轭连接基的苯酚基自由基系统提供了一种新型的γ控制方案的可能性。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号