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首页> 外文期刊>The Journal of Chemical Physics >The Al~+-H2 cation complex:Rotationalty resolved infrared spectrum,potential energy surface,and rovibrationa! calculations
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The Al~+-H2 cation complex:Rotationalty resolved infrared spectrum,potential energy surface,and rovibrationa! calculations

机译：Al〜+ -H2阳离子配合物：解析度的红外光谱，势能面和流动性！计算

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The infrared spectrum of the Al~+-H2 complex is recorded in the H-H stretch region (4075-4110 cm~(-1)) by monitoring Al~+photofragments.The H-H stretch band is centered at 4095.2 cm~(-1),a shift of-66.0 cm-1 from the Q_1(0) transition of the free H2 molecule.Altogether,47 rovibrational transitions belonging to the parallel K_a=0-0 and 1-1 subbands were identified and fitted using a Watson A-reduced Hamiltonian,yielding effective spectroscopic constants.The results suggest that Al~+-H2 has a T-shaped equilibrium configuration with the Al~+ion attached to a slightly perturbed H2 molecule,but that large-amplitude intermolecular vibrational motions significantly influence the rotational constants derived from an asymmetric rotor analysis.The vibrationally averaged intermolecular separation in the ground vibrational state is estimated as 3.03 A,decreasing by 0.03 A when the H2 subunit is vibrationally excited.A three-dimensional potential energy surface for Al~+-H2 is calculated ab initio using the coupled cluster CCSD(T) method and employed for variational calculations of the ro vibrational energy levels and wave functions.Effective dissociation energies for Al~+-H2(para) and Al~+-H2(ortho) are predicted,respectively,to be 469.4 and 506.4 cm~(-1),in good agreement with previous measurements.The calculations reproduce the experimental H-H stretch frequency to within 3.75 cm~(-1),and the calculated B and C rotational constants to within ~2%,Agreement between experiment and theory supports both the accuracy of the ab initio potential energy surface and the interpretation of the measured spectrum.
机译：通过监测Al〜+光致碎裂，在HH拉伸区域（4075-4110 cm〜（-1））记录Al〜+ -H2配合物的红外光谱，HH拉伸带的中心为4095.2 cm〜（-1）。 ，从游离H2分子的Q_1（0）跃迁起66.0 cm-1的位移。总共，确定了47个属于平行K_a = 0-0和1-1子带的旋转振动跃迁，并使用Watson A-结果表明，Al〜+ -H2具有T形的平衡构型，其中Al〜+离子与微扰的H2分子连接，但大幅度的分子间振动会显着影响旋转。由不对称转子分析得出的常数计算的从头算起运用耦合簇CCSD（T）方法，对ro振动能级和波函数进行变分计算。分别预测了Al〜+ -H2（para）和Al〜+ -H2（ortho）的有效离解能，分别为469.4和506.4 cm〜（-1），与之前的测量结果非常吻合。计算结果重现了实验HH拉伸频率在3.75 cm〜（-1）之内，计算出的B和C旋转常数在〜2％之内，实验和理论之间的协议支持从头计算势能面的准确性和所测光谱的解释。

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