Mode‐selective photoisomerization in 5‐hydroxytropolone. II. Theory
Mode‐selective photoisomerization in 5‐hydroxytropolone. II. Theory
复制标题
5-羟基托酚酮 II 的模式选择性光异构化。
DOI：
10.1063/1.469251
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发表时间：
1995
期刊：
影响因子：
--
通讯作者：
K. Jordan
中科院分区：
文献类型：
--
作者：
John J Nash;T. Zwier;K. Jordan
采用从头计算方法研究了5-羟基环庚三烯酚酮（5-HOTrOH）顺-反光异构化反应的基态势能面.确定了两个反应坐标，涉及2-OH隧穿和5-OH扭转。Hartree-Fock（HF）和微扰理论（在MP2水平）已被用于计算与这些坐标相关的二维表面上的驻点。对母体分子环庚三烯酚酮进行类似的计算以供比较。如在先前的研究中所观察到的，2-OH隧穿势垒在包括电子相关的MP2水平下急剧下降。在HF/6 - 31 G ** 和MP2/6 - 31 G ** 水平上对环酚酮和5-HOTrOH进行振动频率计算，以便将模式与实验观察到的模式相关联。介绍了一种方法，用于评估正常的坐标应该是最强耦合到一个给定的反应坐标。标准化，质量加权内在和直接反应c...
Ab initio calculations are used to explore the ground‐state potential energy surface for the syn–anti photoisomerization reaction of 5‐hydroxytropolone (5‐HOTrOH). Two reaction coordinates are identified, involving 2‐OH tunneling and 5‐OH torsion. Hartree–Fock (HF) and perturbation theory (at the MP2 level) have been used to calculate the stationary points on the two‐dimensional surface associated with these coordinates. Similar calculations on the parent molecule tropolone are carried out for comparison. As observed in previous studies, the 2‐OH tunneling barrier drops dramatically at the MP2 level which includes electron correlation. Vibrational frequency calculations are carried out for both tropolone and 5‐HOTrOH at the HF/6‐31G** and MP2/6‐31G** levels in order to correlate the modes with those observed experimentally. A method is introduced for evaluating which normal coordinates should be most strongly coupled to a given reaction coordinate. Normalized, mass‐weighted intrinsic and direct reaction c...