论文标题
甲酸及其剥离形式的分子内振动重新分布
Intramolecular Vibrational Redistribution in Formic Acid and its Deuterated Forms
论文作者
论文摘要
在Richter和Carbonniere的全维势能表面上模拟了甲酸的分子内振动弛豫动力学及其氘代同位素的动力学[F. Richter和P. Carbonniere，J。Chem。 Phys。，148，064303（2018）]使用Heidelberg MCTDH软件包。与捕获大多数反式同异构化的扭转坐标的模式耦合在人工激发的振动模式泛音的动力学中鉴定出来。 C-O伸展明亮的振动模式与HCOOH的隔离扭转模式耦合，在该模式下，可以利用这种耦合来利用激光诱导的TROS-CIS异构化。观察到强大的同位素效应：羟基的暗科和DCOOD的暗氧基团摧毁了C-O伸展到扭转模式耦合，而在DCOOH中，几乎没有观察到任何效果。
The intramolecular vibrational relaxation dynamics of formic acid and its deuterated isotopologues is simulated on the full-dimensional potential energy surface of Richter and Carbonniere [F. Richter and P. Carbonniere, J. Chem. Phys., 148, 064303 (2018)] using the Heidelberg MCTDH package. Mode couplings with the torsion coordinate capturing most of the trans-cis isomerisation are identified in the dynamics of artificially excited vibrational mode overtones. The C-O stretch bright vibrational mode is coupled to the out-of-the plane torsion mode in HCOOH, where this coupling could be exploited for laser-induced trans-to-cis isomerisation. Strong isotopic effects are observed: deuteration of the hydroxyl group, i.e., in HCOOD and DCOOD, destroys the C-O stretch to torsion mode coupling whereas in DCOOH, little to no effect is observed.
