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Non-adiabatic effects in quantum dynamical investigations of nuclei in the collision system H2 + H+, H + H2+ and H3+

碰撞系统 H2 H 、 H H2 和 H3 中原子核量子动力学研究中的非绝热效应

基本信息

批准号：
65676567
负责人：
Professor Dr. Ralph Jaquet
金额：
--
依托单位：
Arbeitsgruppe Theoretische Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2008
资助国家：
德国
起止时间：
2007-12-31 至 2017-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/65676567?language=en
关键词：
Non adiabatic effects quantum dynamical

项目摘要

For the system H3+ (singlet ground state) spectroscopic and scattering investigations will be performed including especially non-adiabatic effects. H3+ is the most important molecule in the field of ion-physics, plasma physics and astrophysics (history of our universe, molecular reactions in the interstellar space and on planets like Jupiter or Saturn) for which it is important to get detailed, highly accurate information about the electron-nuclei dynamics. This includes the following topics: a) bound and excited states and the continuum, b) different electron and nuclear spin states, and c) symmetry-forbidden processes. Based on our global highly accurate potential energy surfaces (PES) for the three lowest electronic states using all necessary couplings between the PESs we want to calculate first the ro-vibrational transition frequencies for the electronic ground state with an accuracy better than 0.01 cm-1. Non-adiabatic effects will be taken care of by two different strategies: (a) use of geometry-dependent effective nuclear masses for the ground state PES, and (b) coupling of several electronic PESs in diabatic or in adiabatic representation. The high accuracy should be gained at least in the ranges of the potential energy surface from the zero-point energy up to slightly below the dissociation energy (perhaps even beyond). The PESs are based on ab initio calculations using the R12 or Gaussian geminal methods, which explicitly take into account the interelectronic distance r_12 in the electronic wavefunction. Corrections to the PESs include the adiabatic and relativistic energy contributions. The non-adiabatic couplings are calculated an ab initio level, too. The same is true for the geometry-dependent nuclear mass-corrections. In the asymptotic region of the PES (region of dissociation) one finds a strong avoided crossing, which leads to couplings of singular type. For that reason, one needs for these regions a nuclear dynamics based on the coupling of several electronic PESs.The investigation of the nuclear dynamics, especially the influence of non-adiabatic effects, will be performed for the whole energy region: from the energy minimum to the region of dissociation energy (spectroscopy) and far beyond (reaction dynamics: from low (ultra-cold) to high collision energy): (a) Spectroscopic investigations from bound states up to resonances(b) Time-independent investigations of ultra-cold processes for the ortho-para conversion of H2 in collision with H+ (single PES),(c) Radiative association of H2 + H+ -> H3+ (stabilization by energy reduction via radiation),(d) Investigation of photodissociation/predissociation of H3+ around the dissociation energy, and(e) Time-dependent investigations of the charge exchange processes in the collision of H2 + H+ using coupled PESs (collision energies >1.8eV).

对于系统 H3+（单态基态），将进行光谱和散射研究，尤其包括非绝热效应。 H3+ 是离子物理学、等离子体物理学和天体物理学（宇宙的历史、星际空间以及木星或土星等行星上的分子反应）领域最重要的分子，获得有关电子核动力学的详细、高度准确的信息非常重要。这包括以下主题：a）束缚态和激发态以及连续体，b）不同的电子和核自旋态，以及c）对称禁止过程。基于我们对三个最低电子态的全局高精度势能面 (PES)，使用 PES 之间的所有必要耦合，我们希望首先计算电子基态的旋转振动跃迁频率，精度优于 0.01 cm-1。非绝热效应将通过两种不同的策略来处理：（a）使用几何相关的有效核质量作为基态 PES，以及（b）以非绝热或绝热表示形式耦合多个电子 PES。至少在从零点能量到略低于解离能（也许甚至超出）的势能面范围内应该获得高精度。 PES 基于使用 R12 或高斯孪生方法的从头计算，明确考虑了电子波函数中的电子间距离 r_12。对 PES 的修正包括绝热和相对论能量贡献。非绝热耦合也是从头开始计算的。对于依赖于几何形状的核质量校正也是如此。在 PES（解离区）的渐近区域中，人们发现了强烈的避免交叉，这导致了奇异类型的耦合。因此，这些区域需要基于多个电子 PES 耦合的核动力学。核动力学的研究，特别是非绝热效应的影响，将针对整个能量区域进行：从能量最小值到解离能区域（光谱学）以及更远的区域（反应动力学：从低（超冷）到高碰撞能）：（a）从束缚态到最高能量的光谱研究 (b) H2 与 H+ 碰撞时邻位-对位转化的超冷过程的与时间无关的研究（单 PES），(c) H2 + H+ -> H3+ 的辐射缔合（通过辐射降低能量来稳定），(d) 研究解离能周围 H3+ 的光解离/预解离，以及(e) 电荷交换的时间依赖性研究使用耦合 PES（碰撞能量 >1.8eV）进行 H2 + H+ 碰撞过程。