Development of time-dependent density functional theory for electronic and nuclear degrees of freedom : Investigation of structural deformation of molecules in intense laser fields

电子和核自由度的时间相关密度泛函理论的发展：强激光场中分子结构变形的研究

• 批准号: 14540463
• 负责人: KONO Hirohiko
• 金额: $ 2.11万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540463/
• 关键词: time-dependent density functional theory; electronic wave packet; nuclear wave packet; time-dependent adiabatic state; hydrogen molecular ion; selective bond dissociation; nonadiabatic transition; correlation potential; 時断依存断熱状態

We developed a dual transformation method that is applicable to multicomponent density functional theory. The model of a multicomponent system is chosen to be H_2^+. The energy and the geometry of the ground state are calculated by using the finite difference method based on multicomponent density functional theory. The results obtained were compared with those obtained from the Born-Oppenheimer approximation and those obtained by exact treatment. The real-time dynamics of H_2^+ are also demonstrated. The results obtained are discussed and compared with the exact solution. The importance of the dynamic correlation effect between nuclei and an electron is clearly shown. We also present a nucleus-electron gas model to estimate the nucleus-electron correlation energy. The expression of the effective interaction between nucleus and electron in the framework of the random-phase approximation is derived. We find that the attractive interaction between nucleus and electron can be shielded. Th … More e expression of the perturbation energy within the ladder approximation is also derived. We present a numerical procedure to calculate the correlation energy and the correlation potential between nucleus and electron, and estimate the nucleus-electron correlation potential.To examine the validity of the above methods, we developed a reference method, namely, the time-dependent adiabatic state approach, in which the electronic and nuclear dynamics in a near-infrared field is described in terms of time-dependent adiabatic potentials and nonadiabatic transitions due to temporal change in the laser electric field. The properties of the adiabatic states of polyatomic molecules can be calculated by ab initio molecular orbital methods. We applied the proposed approach to dynamics of CO_2 in near-infrared intense fields and revealed that in the CO_2^<2+> stage, simultaneous symmetric two-bond stretching followed by the occurrence of a large-amplitude bending motion is induced by an intense field. We also reported the results of theoretical investigation of experimentally observed selective cleavage of C-O and C-C bonds of ethanol in intense laser fields. Less

我们发展了一种适用于多组分密度泛函理论的对偶变换方法。多组分体系的模型选择为H_2^+。用基于多组分密度泛函理论的有限差分方法计算了基态的能量和几何构型。所得结果与Born-Oppenheimer近似和精确处理所得结果进行了比较。H_2^+的实时动力学也被演示。所得结果进行了讨论，并与精确解进行了比较。这清楚地表明了原子核与电子之间的动态关联效应的重要性。我们还提出了一个核-电子气模型来估计核-电子相关能。在无规相位近似下，导出了核与电子有效相互作用的表达式。我们发现，原子核和电子之间的吸引相互作用可以被屏蔽。日 ...更多信息 在梯形近似下，导出了微扰能的表达式。本文给出了计算核-电子关联能和关联势以及核-电子关联势的数值方法，并发展了一种参考方法，即含时绝热态方法，其中近红外场中的电子和核动力学是根据时间来描述的，依赖的绝热势和非绝热跃迁，由于激光电场的时间变化。用从头算分子轨道方法可以计算多原子分子绝热态的性质。我们将所提出的方法应用于近红外强场中CO_2的动力学，发现在CO_2^<2+>阶段，强场诱导同时发生对称的双键伸缩，随后发生大幅度的弯曲运动.我们还报道了在强激光场中乙醇的C-O键和C-C键选择性断裂的实验观察结果。少

项目成果

Y.Sato, H.Kono, S.Koseki, Y.Fujimura: "Description of molecular dynamics in intense laser fields by the time-dependent adiabatic state approach : Application to simultaneous two bond dissociation of CO_2 and its control"Journal of American Chemical Societ

Y.Sato、H.Kono、S.Koseki、Y.Fujimura：“通过依赖时间的绝热态方法描述强激光场中的分子动力学：应用于 CO_2 的同时二键解离及其控制”美国化学杂志

J.Ohkubo, T.Kato, H.Kono, Y.Fujimura: "Molecular alignment in a liquid induced by a nonresonant laser field : Molecular dynamics simulation"Journal of Chemical Physics. 120・19. 9123-9132 (2004)

J.Ohkubo、T.Kato、H.Kono、Y.Fujimura：“非共振激光场引起的液体中的分子排列：分子动力学模拟”化学物理杂志 120・19（2004）。

T.Kato, H.Kono: "Time-dependent multiconfiguration theory for electronic dynamics of molecules in an intense laser field"Chemical Physics Letters. (in press). (2004)

T.Kato、H.Kono：“强激光场中分子电子动力学的时间相关多构型理论”《化学物理快报》。

K.Harumiya, H.Kono: "Intense laser field ionization of H_2 enhanced by two-electron dynamics"Physical Review A. 66・4. 043403-1-043403-14 (2002)

K.Harumiya、H.Kono：“通过双电子动力学增强 H_2 的强激光场电离”物理评论 A. 66・4。 043403-1-043403-14 (2002)

Y.Kato, H.Kono: "Time-dependent multiconfiguration theory for electronic dynamics of molecules in an intense laser field"Chemical Physics Letters. (in press). (2004)

Y.Kato、H.Kono：“强激光场中分子电子动力学的时间相关多构型理论”《化学物理快报》。