论文标题
甲酸二聚体的指纹区域：曲线坐标中的变异振动计算
Fingerprint region of the formic acid dimer: variational vibrational computations in curvilinear coordinates
论文作者
论文摘要
曲线性动能模型是针对多种核运动计算开发的，包括甲酸二聚体的间隔和低分子内部自由度。通过求解一系列振动模型的振动schrödinger方程，研究了一系列振动模型的耦合，通过选择各种活动模式和约束坐标值的组合，从两个到十个活动振动的自由度。振动状态，节点分配和红外振动强度信息是使用Qu和Bowman开发的全维势能表面（PES）和电偶极矩表面计算的。化学化学物理。 18，24835（2016）; J. Chem。物理。 148，241713（2018）]。与喷气冷却的振动光谱实验相比，几个基本和组合频段获得了良好的效果，但是对$ν_8$和$ν_9$基本振动的描述在能量上接近并且具有相同的对称性，似乎是有问题的。对于与实验相比的进一步进展，势能表面，尤其是其多维耦合表示需要进一步改进。
Curvilinear kinetic energy models are developed for variational nuclear motion computations including the inter- and the low-frequency intra-molecular degrees of freedom of the formic acid dimer. The coupling of the inter- and intra-molecular modes is studied by solving the vibrational Schrödinger equation for a series of vibrational models, from two up to ten active vibrational degrees of freedom by selecting various combinations of active modes and constrained coordinate values. Vibrational states, nodal assignment, and infrared vibrational intensity information is computed using the the full-dimensional potential energy surface (PES) and electric dipole moment surface developed by Qu and Bowman [Phys. Chem. Chem. Phys. 18, 24835 (2016); J. Chem. Phys. 148, 241713 (2018)]. Good results are obtained for several fundamental and combination bands in comparison with with jet-cooled vibrational spectroscopy experiments, but the description of the $ν_8$ and $ν_9$ fundamental vibrations, which are close in energy and have the same symmetry, appears to be problematic. For further progress in comparison with experiment, the potential energy surface, and in particular, its multi-dimensional couplings representation, requires further improvement.
