C_2H_2分子S_1态顺反异构化反应的降维DVR研究
Reduced Dimension DVR Study of cis-trans Isomerization in the S_1 State of C_2H_2
摘要：
用降维DVR方法研究了乙炔分子S1态顺反异构体的异构化反应。现有的DVR技术相结合的高精度势能面和动能运营商来自FG理论产生一个有效的，但简单的哈密顿量治疗大幅度运动。S1异构化的光谱特征进行了讨论，重点是振动方面。异构化低势垒的存在导致反式振动能级结构的畸变，并出现名义上电子禁戒的<$A2 \leftarrow X 1 <$+g跃迁到顺式构象异构体的振动能级。这两种效应的模型与实验结果一致，并阐明了隧道效应和状态混合的基本机制，通过使用计算的振动波函数。
英文摘要：
Isomerization between the cis and trans conformers of the S1 state of acetylene is studied using a reduced dimension DVR calculation. Existing DVR techniques are combined with a high accuracy potential energy surface and a kinetic energy operator derived from FG theory to yield an effective but simple Hamiltonian for treating large amplitude motions. The spectroscopic signatures of the S1 isomerization are discussed, with emphasis on the vibrational aspects. The presence of a low barrier to isomerization causes distortion of the trans vibrational level structure and the appearance of nominally electronically forbidden Ã1A2 \leftarrow X 1Σ+g transitions to vibrational levels of the cis conformer. Both of these effects are modeled in agreement with experimental results, and the underlying mechanisms of tunneling and state mixing are elucidated by use of the calculated vibrational wavefunctions.
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