CH_3F-Rg体系四维势能面及其振转光谱预测
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- 英文论文题名：The 4D potential energy surface and predicted ro-vibrational spectra for CH_3F-Rg systems
- 论文作者：马永涛 ; 李辉
- 英文论文作者：Yong-Tao Ma ; Hui Li ; Institute of Theoretical Chemistry ; Jilin University ; Institute of Theoretical Chemistry ; Jilin University
- 年：2016
- 作者机构：吉林大学理论化学研究所;
- 论文关键词：CH3F-Rg ; 高精度势能面 ; 振转光谱
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十九分会：化学中的量子与经典动力学
- 语种：中文
- 分类号：O644.1
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十九分会 ; 化学中的量子与经典动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：142k
- 原文格式：D
- 会议级别：全国
摘要
本工作报道了CH_3F-Rg(Rg=He、Ne、Ar)体系包含CH_3F分子红外活性强的C-F伸缩的振动四维高精度势能面。这些体系振动平均后的势能面通过非线性拟合成摩斯长程势(MLR)形式。[1]拟合的标准差均小于0.1个波数。这三个体系的势能面都存在一个T-型结构的最小值点和两个局部最小值点以及两个过渡态。势能面的能量值、阱深和能垒大小均按CH_3F-He、CH_3F-Ne和CH_3F-Ar排列。随后,这些势能面被运用于体系的能级计算中。我们用分子对称群理论去构造体系的包含对称性的波函数,用联合离散变量表象和有限基组表象的方法生成其矩阵元,用Lanczos迭代方法求解体系的薛定谔方程。[2]基于波函数分析,我们指认了体系的能级并根据选择定则预测了体系的红外、微波光谱。这些光谱的跃迁强度也通过理论计算给出。
In this work, we reported the four-dimensional ab initio intermolecular potential energy surfaces for CH_3F-Rg(Rg=He,Ne,Ar) systems that explicitly incorporates dependence on the C-F stretching normal node of the CH_3F molecule. Analytical three-dimensional PESs for these systems are obtained by least-squares fitting the vibrationally averaged potentials to the Morse/Long-Range potential function form. One T-shaped global minimum and two global minimums are found in these PESs. The energy, well depth and the barriers are arranged by CH_3F-He, CH_3F-Ne and CH_3F-Ar. With the 3D PESs, we employ Lanczos algorithm to calculate ro-vibrational levels of the dimer system. In detail, we use molecule symmetry group theory to get parity-adapted basis, use combined DVR and FBR method to produce the matrix elements. Base on the wavefunction analysis, we assign the energy levels. Use the knowledge of selection rule, we predict the microwave and infrared spectra of these systems. The transition intensities of these spectra are also given.
In this work, we reported the four-dimensional ab initio intermolecular potential energy surfaces for CH_3F-Rg(Rg=He,Ne,Ar) systems that explicitly incorporates dependence on the C-F stretching normal node of the CH_3F molecule. Analytical three-dimensional PESs for these systems are obtained by least-squares fitting the vibrationally averaged potentials to the Morse/Long-Range potential function form. One T-shaped global minimum and two global minimums are found in these PESs. The energy, well depth and the barriers are arranged by CH_3F-He, CH_3F-Ne and CH_3F-Ar. With the 3D PESs, we employ Lanczos algorithm to calculate ro-vibrational levels of the dimer system. In detail, we use molecule symmetry group theory to get parity-adapted basis, use combined DVR and FBR method to produce the matrix elements. Base on the wavefunction analysis, we assign the energy levels. Use the knowledge of selection rule, we predict the microwave and infrared spectra of these systems. The transition intensities of these spectra are also given.
引文
[1]R.J.Le Roy;R.D.E.Henderson.Mol.Phys.2007,105:663.
[2]C.Lanczos.J Res Natl Bur Stand.1950,45:255.
[2]C.Lanczos.J Res Natl Bur Stand.1950,45:255.