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

对于系统H3+（单线态基态），将进行光谱和散射研究，特别是包括非绝热效应。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、星际空间和木星或土星等行星上的分子反应）领域中最重要的分子，因此获得有关电子-原子核动力学的详细、高度精确的信息非常重要。这包括以下主题：a)束缚态和激发态以及连续统，b)不同的电子和核自旋态，以及c)对称禁止过程。基于我们的三个最低电子态的全球高精度势能面（PES），利用所有必要的势能面之间的耦合，我们希望首先计算电子基态的反振动跃迁频率，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)对基态PES使用几何相关的有效核质量，以及(b)以绝热或绝热表示的几个电子ps的耦合。至少在从零点能到略低于解离能（甚至可能超过）的势能面范围内，应获得高精度。PESs基于从头计算，使用R12或高斯二代方法，明确地考虑了电子波函数中的电子间距离r_12。对ps的修正包括绝热和相对论能量的贡献。非绝热耦合也从从头算起。与几何相关的核质量修正也是如此。在PES（解离区）的渐近区域，人们发现了一个强避免交叉，这导致了奇异型耦合。因此，这些区域需要基于几个电子ps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，将在整个能量区域进行：从能量最小到离解能区域（光谱学），甚至更远（反应动力学：从低（超冷）到高碰撞能）。(a)从束缚态到共振态的光谱研究(b) H2与H+碰撞的正交对位转化超冷过程的时间无关研究（单PES），(c) H2 + H+ -> H3+的辐射缔合（通过辐射降低能量来稳定），(d) H3+在解离能附近的光解/预解研究。(e)利用耦合PESs（碰撞能量>1.8eV）研究H2 + H+碰撞中电荷交换过程的时间依赖性。

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).