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

对于该系统，将进行H~(3+)(单重态)光谱和散射研究，特别是包括非绝热效应。H3+是离子物理、等离子体物理和天体物理(我们的宇宙历史、星际空间中的分子反应以及木星或土星等行星上的分子反应)领域中最重要的分子，对这些领域来说，获得关于电子-核动力学的详细、高度准确的信息是很重要的。这包括以下主题：a)束缚态和激发态以及连续体，b)不同的电子自旋态和核自旋态，以及c)对称禁止过程。基于我们的全球最低三个电子态的高精度势能面，利用势能面之间所有必要的耦合，我们想要首先计算电子基态的振动跃迁频率，精度优于0.01厘米-1。非绝热效应将通过两种不同的策略来处理：(A)使用与几何有关的有效核质量来处理基态PES，以及(B)在非绝热或绝热表示下几个电子PES的耦合。至少在从零点能到略低于离解能(甚至更高)的势能面范围内，应该获得高的精度。该方法基于从头算方法，采用R12或高斯基元方法，在电子波函数中显式考虑了电子间距离r12。对PESS的修正包括绝热和相对论能量贡献。非绝热耦合也是在从头算水平上计算的。同样的道理也适用于几何相关的核质量修正。在解离区的渐近区域，我们发现了一个强的回避交叉，这导致了奇异型的耦合。因此，对于这些区域，人们需要一个基于多个电子电子态耦合的核动力学。核动力学的研究，特别是非绝热效应的影响，将在整个能区进行：从能量最低到解离能(光谱)以及更远的区域(反应动力学：从低(超冷)到高碰撞能)：(A)从束缚态到共振的光谱研究(B)氢与H+碰撞的正对位转化的超冷过程的时间无关的研究(单个PES)，(C)H2+H+-&GT的辐射缔合；(D)H~(3+)在离解能附近的光解/预解离的研究，以及(E)用耦合电子能谱(碰撞能，1.8 eV)研究H~+与H~+碰撞过程中的电荷交换过程。

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).