HCl-H2O dimer: an accurate full-dimensional potential energy surface and fully coupled quantum calculations of intra- and intermolecular vibrational states and frequency shifts.
HCl-H2O dimer: an accurate full-dimensional potential energy surface and fully coupled quantum calculations of intra- and intermolecular vibrational states and frequency shifts.
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DOI：
10.1039/d1cp00865j
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发表时间：
2021-03
期刊：
影响因子：
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通讯作者：
Yang Liu;Jun Li;P. Felker;Z. Bačić
中科院分区：
文献类型：
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作者：
Yang Liu;Jun Li;P. Felker;Z. Bačić
HCl和H2O之间的相互作用是相当大的理论和实验的兴趣，由于其在大气化学中的重要作用和理解的HCl在水中的解离的开始。在这项工作中，HCl-H2O复合物的定量特征在于在两个方面。首先，我们报道了HCl + H_2O体系的一个新的全维势能面（PES）。九维（9D）PES基于CCSD（T）-F12 a/AVTZ水平上计算的约43 000个从头算点，采用置换不变多项式-神经网络方法进行基组叠加误差校正，可以准确有效地再现HCl与H2O络合物的几何构型、能量、频率以及相关的最小能量路径。我们提出的第一个完全耦合的9D量子计算的内部和分子间的振动态的HCl-H2O二聚体，进行新的PES的结果。他们采用了以前用于精确计算H2O/D2 O-CO和HDO-CO复合物的振转能级结构的高效束缚态方法[P.M. Felker和Z. Bačić，J. Chem. Phys.，2020，153，074107; J. Phys. Chem. A，2021，125，980]。9D计算表征的振动平均的非平面基态几何的HCl-H2O复合物，H2O和HCl部分的分子内振动的基本原理，和它们的频率偏移，以及低能量的分子间的振动状态在每个分子内的振动流形和两组模式之间的耦合的影响。HCl-H2O二聚体的计算性质与现有的光谱数据非常吻合。9D计算的二聚体结合能D 0为1334.63 cm-1，与实验D 0（1334 ± 10 cm-1）非常吻合[B. E. Casterline和A. K. Mollner和L. C. Chng和H. Reisler，J. Chem. Phys.，2010，114，9774]。此外，由9D计算得到的H_2O离面弯曲角的基态期望值为33.80°，HCl伸缩频移为-157.9 cm ~（-1），与相应的实验值雅阁很好.
The interaction between HCl and H2O is of considerable theoretical and experimental interest due to its important role in atmospheric chemistry and understanding the onset of the dissociation of HCl in water. In this work, the HCl-H2O complex is quantitatively characterized in two ways. First, we report a new full-dimensional potential energy surface (PES) for the HCl + H2O system. The nine-dimensional (9D) PES is based on circa 43 000 ab initio points calculated at the level of CCSD(T)-F12a/AVTZ with the basis set superposition error correction using the permutation invariant polynomial-neural network method, which can accurately and efficiently reproduce the geometries, energies, frequencies of the complex of HCl with H2O, as well as the relevant minimum energy path. Next, we present the results of the first fully coupled 9D quantum calculations of the intra- and intermolecular vibrational states of the HCl-H2O dimer, performed on the new PES. They employ the highly efficient bound-state methodology previously used to compute accurately the rovibrational level structure of the H2O/D2O-CO and HDO-CO complexes [P. M. Felker and Z. Bačić, J. Chem. Phys., 2020, 153, 074107; J. Phys. Chem. A, 2021, 125, 980]. The 9D calculations characterize the vibrationally averaged nonplanar ground-state geometry of the HCl-H2O complex, the intramolecular vibrational fundamentals of both H2O and HCl moieties, and their frequency shifts, as well as the low-energy intermolecular vibrational states in each of the intramolecular vibrational manifolds and the effects of the coupling between the two sets of modes. The calculated properties of the HCl-H2O dimer are in excellent agreement with the available spectroscopic data. The 9D computed dimer binding energy D0 of 1334.63 cm-1 agrees extremely well with the experimental D0 equal to 1334 ± 10 cm-1 [B. E. Casterline and A. K. Mollner and L. C. Ch'ng and H. Reisler, J. Chem. Phys., 2010, 114, 9774]. Moreover, the ground-state expectation value of the out-of-plane bend angle of H2O, 33.80°, and the computed HCl stretch frequency shift, -157.9 cm-1, both from the 9D calculations, are in very good accord with the corresponding experimental values.