The vibrational eigenenergies of the deuterated forms of formic acid (DCOOD, HCOOD, and DCOOH) have been computed using the block-improved relaxation method, as implemented in the Heidelberg multiconfiguration time-dependent Hartree package on a previously published potential energy surface [F. Richter and P. Carbonnière, J. Chem. Phys. 148, 064303 (2018)] generated at the CCSD(T)-F12a/aug-cc-pVTZ-F12 level of theory. Fundamental, combination band, and overtone transition frequencies of the trans isomer were computed up to ∼3000 cm-1 with respect to the zero point energy, and assignments were determined by visualization of the reduced densities. Root mean square deviations of computed fundamental transition frequencies with experimentally available gas-phase measurements are 8, 7, and 3 cm-1 for trans-DCOOD, trans-HCOOD, and trans-DCOOH, respectively. The fundamental transition frequencies are provided for the cis isomer of all deuterated forms; experimental measurements of these frequencies for the deuterated cis isotopologues are not yet available, and the present work may guide their identification.

中文翻译：

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氘代反式和顺式甲酸的振动状态：DCOOH，HCOOD和DCOOD。

氘化形式的甲酸（DCOOD，HCOOD和DCOOH）的振动本征能已使用块改进的弛豫方法进行了计算，该方法在以前发布的势能面的海德堡多组态时变Hartree软件包中实现。Richter和P.Carbonnière，化学杂志。物理 148，064303（2018）]在CCSD（T）-F12a / aug-cc-pVTZ-F12理论水平上生成。相对于零点能量，计算反式异构体的基本，组合带和泛音跃迁频率高达〜3000 cm-1，并通过可视化降低的密度确定分配。对于反式-DCOOD，反式-HCOOD和反式-DCOOH，通过实验可获得的气相测量值计算出的基本跃迁频率的均方根偏差为8、7和3 cm-1，分别。提供了所有氘代形式的顺式异构体的基本跃迁频率；氘化的顺式同位素异构体的这些频率的实验测量尚不可用，目前的工作可能会指导它们的鉴定。