System-environment interaction and ultrafast dynamical processes involving conical intersections

涉及圆锥形交叉点的系统-环境相互作用和超快动态过程

• 批准号: 23385399
• 负责人: Professor Dr. Horst Köppel
• 金额: --
• 依托单位: Forschungsgruppe Theoretische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2006
• 资助国家: 德国
• 起止时间: 2005-12-31 至 2010-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/23385399?language=en
• 关键词: System; environment; interaction; ultrafast; dynamical

Conical intersections, a particular topology of intersecting electronic potential energy surfaces, play a key role in the photochemistry of many molecular systems, where they represent a paradigm for ultrafast internal conversion phenomena. While their impact on the quantum dynamics of small isolated species is well known, very few studies have been dedicated to large isolated polyatomic systems or system-environment complexes, where an intra or intermodular environment is expected to strongly influence the dynamics at conical intersections. This project focuses on methodological developments to describe the dynamics through conical intersections in macrosystems. These developments are based on two recent advances in the group: the elaboration of an effective-mode formulation, suitable to describe the short-time dynamics through conical intersections in macrosystems, and the derivation of an efficient way of constructing diabatic states appropriate for multidimensional quantum-dynamical calculations. It is the development and combination of these advances, to go for the first time to an accurate description of the quantum dynamics through conical intersections in macrosystems, which constitute the objectives of this project. Applications to challenging molecular systems are planned.

锥形交叉点，交叉电子势能面的一种特殊拓扑结构，在许多分子系统的光化学中起着关键作用，它们代表了超快内转换现象的范例。虽然它们对小孤立物种量子动力学的影响是众所周知的，但很少有研究致力于大型孤立多原子系统或系统-环境复合物，其中内部或模块间环境预计会强烈影响圆锥交叉点的动力学。这个项目的重点是方法的发展，以描述动态通过圆锥相交的宏观系统。这些发展是基于两个最新的进展，在该组：一个有效的模式制定，适合于描述短时间的动态通过圆锥形的交叉点在宏观系统的阐述，并推导出一种有效的方式来构建适合于多维量子动力学计算的非绝热状态。正是这些进展的发展和结合，第一次通过宏观系统中的圆锥相交精确描述了量子动力学，这构成了该项目的目标。计划应用于具有挑战性的分子系统。

项目成果

Quantum dynamics through conical intersections: combining effective modes and quadratic couplings.

通过圆锥相交的量子动力学：结合有效模式和二次耦合

• DOI: 10.1021/jp2068528
• 发表时间: 2012
• 期刊: The journal of physical chemistry. A
• 作者: A. Vibok;A. Csehi;E. Gindensperger;H. Köppel;G. Halász
• 通讯作者: G. Halász

Efficient computation of adiabatic electronic populations in multi-mode vibronic systems: theory, implementation, and application.

多模电子振动系统中绝热电子布居的有效计算：理论、实现和应用

• DOI: 10.1063/1.4753966
• 发表时间: 2012
• 期刊: The Journal of chemical physics
• 作者: B. Nikoobakht;H. Köppel;E. Gindensperger;L. S. Cederbaum
• 通讯作者: L. S. Cederbaum

Short-time dynamics through conical intersections in macrosystems.

• DOI: 10.1007/978-94-007-2076-3_16
• 发表时间: 2005-03
• 期刊: Physical review letters
• 影响因子: 8.6
• 作者: L. Cederbaum;E. Gindensperger;I. Burghardt