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Complex between Formic Acid and Nitrous Oxide: A Matrix-Isolation and Computational Study
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.jpca.7b09586 Luís Duarte 1 , Iiris Rekola 1 , Leonid Khriachtchev 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.jpca.7b09586 Luís Duarte 1 , Iiris Rekola 1 , Leonid Khriachtchev 1
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The complex of formic acid (FA, HCOOH) with nitrous oxide (N2O) was studied experimentally and computationally. Eight structures of the trans-FA···N2O complex and nine structures of the cis-FA···N2O complex were found at the density functional theory (M06-2X and wB97XD), MP2(full), and CCSD(T)-F12a levels. Two structures of the trans-FA···N2O complex (1t and 3t) and two structures of the cis-FA···N2O complex (1c and 3c) were identified by infrared spectroscopy in an argon matrix. Structure 1t with the bonded OH group appears in the matrices after deposition. Structures 3t and 3c with the free OH groups were prepared by vibrational excitation of the trans-FA conformer in structures 1t and 3t, respectively. Structure 3t is thermally unstable and relaxes to structure 1t at ∼15 K. Structure 1c with the bonded OH group is made by vibrational excitation of trans-FA monomer combined with thermal annealing. The lifetimes of the cis-FA···N2O complex structures 1c (81.5 min) and 3c (18.7 min) in an argon matrix at 4.3 K are longer than that of cis-FA monomer (6.3 min). This difference agrees with the calculated stabilization barriers of these species.
中文翻译：
甲酸和一氧化二氮之间的配合物：基质分离和计算研究
通过实验和计算研究了甲酸（FA，HCOOH）与一氧化二氮（N 2 O）的配合物。所述的八个结构反-FA ...Ñ 2层所述的O复合和九个结构CIS -FA ...Ñ 2在密度泛函理论（M06-2X和wB97XD），MP2（全）被发现O复合，并CCSD（T）-F12a级。在氩气基质中通过红外光谱鉴定了反式-FA··N 2 O配合物的两种结构（1t和3t）和顺式-FA··N 2 O配合物的两种结构（1c和3c）。结构沉积后，1t带有键合的OH基团出现在基体中。通过振动激发结构1t和3t中的反式-FA构象体分别制备具有游离OH基的结构3t和3c。结构3t是热不稳定的，在〜15 K时松弛到结构1t。具有键合OH基的结构1c是通过反式-FA单体的振动激发结合热退火而制得的。顺式-FA···N 2 O复杂结构1c（81.5分钟）和3c的寿命在4.3 K的氩气基质中（18.7分钟）比顺式-FA单体（6.3分钟）更长。这种差异与这些物种的稳定壁垒相符。
更新日期：2017-11-08
中文翻译：
甲酸和一氧化二氮之间的配合物：基质分离和计算研究
通过实验和计算研究了甲酸（FA，HCOOH）与一氧化二氮（N 2 O）的配合物。所述的八个结构反-FA ...Ñ 2层所述的O复合和九个结构CIS -FA ...Ñ 2在密度泛函理论（M06-2X和wB97XD），MP2（全）被发现O复合，并CCSD（T）-F12a级。在氩气基质中通过红外光谱鉴定了反式-FA··N 2 O配合物的两种结构（1t和3t）和顺式-FA··N 2 O配合物的两种结构（1c和3c）。结构沉积后，1t带有键合的OH基团出现在基体中。通过振动激发结构1t和3t中的反式-FA构象体分别制备具有游离OH基的结构3t和3c。结构3t是热不稳定的，在〜15 K时松弛到结构1t。具有键合OH基的结构1c是通过反式-FA单体的振动激发结合热退火而制得的。顺式-FA···N 2 O复杂结构1c（81.5分钟）和3c的寿命在4.3 K的氩气基质中（18.7分钟）比顺式-FA单体（6.3分钟）更长。这种差异与这些物种的稳定壁垒相符。
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