对苯二酚分子反式和顺式构象的对称特性、某些振动能级的隧道分裂和扭转红外光谱

IF 1.4 4区 物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
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引用次数: 0

摘要

根据分子对称组 D2H(M)的不可还原表象,对分别属于对苯二酚分子点对称组 C2H 和 C2V 的反式和顺式构象的扭转振动状态进行了分类。D2H(M) 组的对称元素与二维表面势能、波函数、动力学系数和偶极矩投影的扭转坐标平面上的对称元素之间建立了对应关系。在点对称组 C2H、C2V 的对称种类与分子对称组 D2H(M)的对称种类之间建立了对应关系。在 MP2/Aug-cc-pVDZ、MP2/Aug-cc-pVQZ、MP2/Aug-cc-pVTZ、MP2/CBS(aD,aT,aQ) 和 CCSD(T)/dAug-cc-pVDZ 理论水平上计算了对苯二酚分子的构象状态、内旋转障碍和上述特征。计算出的数据集使用对称适配的基函数集进行近似。通过对限制维数的振动薛定谔方程进行数值求解,首次确定了对苯二酚分子的 50 个静止扭转态的能量和波函数。还确定了反式和顺式构象的基振态和一些激发扭转态的隧道分裂值。特别是,在 MP2/CBS(aD,aT,aQ)理论水平上计算时,反式和顺式构象的地面振动态的隧道分裂值分别为 1.32*10-6 和 1.62*10-6 cm-1,这与 [W. Caminati, S. Meland] 等人通过实验确定的顺式构象的该值上限一致。Caminati、S. Melandri、L. B. Favero,J.Chem.Phys.,100 (1994) 8569 - 8572]的作者为顺式-构象器中的这一数值确定的上限(0.2 MHz 或 6.67*10-6 cm-1)相一致。通过计算偶极矩算子的矩阵元素和分配函数,可以模拟分子构象在不同温度下的扭转红外光谱。在 MP2/CBS(aD,aT,aQ)理论水平上计算出的反式-(267.1 和 269.0 cm-1)和顺式-(269.5 和 270.9 cm-1)构象中的基本扭转振动频率与 [W.G. Fateley, G.L. Carlson, F.F. Bentley, J.Phys.Chem., 79 (1975) 199-204.] 中确定的该振动频率的实验值 (266 cm-1) 非常吻合。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Symmetry properties, tunneling splittings of some vibrational energy levels and torsional IR spectra of the trans – and cis – conformers of hydroquinone molecule

Symmetry properties, tunneling splittings of some vibrational energy levels and torsional IR spectra of the trans – and cis – conformers of hydroquinone molecule

Torsional vibrational states of trans − and cis − conformers belonging to point symmetry groups C2H and C2V, respectively, of hydroquinone molecules are classified according to the irreducible representations of the molecular symmetry group D2H(M). A correspondence has been established between the symmetry elements of the D2H(M) group and the symmetry elements on the torsional coordinate plane for two-dimensional surfaces of potential energy, wave functions, kinetic coefficients and dipole moment projections. A correspondence has been established between the symmetry species of the point symmetry groups C2H, C2V and the symmetry species of the molecular symmetry group D2H(M). Conformational states, barriers to internal rotation and the above-mentioned characteristics of the hydroquinone molecule were calculated at the MP2/Aug-cc-pVDZ, MP2/Aug-cc-pVQZ, MP2/Aug-cc-pVTZ, MP2/CBS(aD,aT,aQ), and CCSD(T)/dAug-cc-pVDZ levels of theory. The calculated data sets were approximated using symmetry-adapted sets of basis functions. Using a numerical solution of the vibrational Schrödinger equation of restricted dimensionality, the energies and wave functions of 50 stationary torsional states of the hydroquinone molecule were determined for the first time. The values of tunneling splittings of the ground vibrational and a number of excited torsional states of trans − and cis − conformers were determined. In particular, when calculating at the MP2/CBS(aD,aT,aQ) level of theory, the values of tunneling splittings of the ground vibrational states of trans − and cis − conformers turned were 1.32*10-6 and 1.62*10-6 cm−1, which is consistent with the experimentally established upper limit for this value in the cis − conformer by authors of [W. Caminati, S. Melandri, L. B. Favero, J.Chem.Phys., 100 (1994) 8569 – 8572] (0.2 MHz or 6.67*10-6 cm−1). The calculations of the matrix elements of the dipole moment operator and the partition function made it possible to simulate the torsional IR spectra of the molecule’s conformers at different temperatures. The frequencies of fundamental torsional vibrations in the trans – (267.1 and 269.0 cm−1) and cis – (269.5 and 270.9 cm−1) conformers, calculated at the MP2/CBS(aD,aT,aQ) level of theory, are in good agreement with the experimental value of frequency of this vibration (266 cm−1), established in [W.G. Fateley, G.L. Carlson, F.F. Bentley, J.Phys.Chem., 79 (1975) 199–204.].

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来源期刊
CiteScore
2.70
自引率
21.40%
发文量
94
审稿时长
29 days
期刊介绍: The Journal of Molecular Spectroscopy presents experimental and theoretical articles on all subjects relevant to molecular spectroscopy and its modern applications. An international medium for the publication of some of the most significant research in the field, the Journal of Molecular Spectroscopy is an invaluable resource for astrophysicists, chemists, physicists, engineers, and others involved in molecular spectroscopy research and practice.
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