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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Infrared spectra and quantum chemical characterization of weakly bound clusters of the benzoyl cation with Ar and H2O
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Infrared spectra and quantum chemical characterization of weakly bound clusters of the benzoyl cation with Ar and H2O

机译：带有Ar和H2O的苯甲酰基阳离子的弱键簇的红外光谱和量子化学表征

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摘要

Weakly-bound clusters of the closed-shell benzoyl cation (C6H5CO~+ , PhCO~+) with Ar and H2O are investigated by infrared (IR) spectroscopy, mass spectrometry, and quantum chemical calculations in order to characterize the interaction of a closed shell aromatic cation with a nonpolar and a polar ligand. PhCO~+-L dimers are produced by electron ionization of benzaldehyde in a supersonic plasma expansion. IR photodissociation (IRPD) spectra of PhCO~+-L with L = Ar and H2O are analyzed in the C-O, C-H, and O-H stretch ranges (2000-3900 cm~(-1)). The potential energy surface of the PhCO~+-L dimers is characterized at the MP2/6-311++G(2df,2pd) level to locate the various minima and determine their energetic and vibrational properties. PhCO~+-Ar prefers intermolecular π-bonding to the aromatic ring with a bond energy of D_0 = 6 kJ mol~(-1). The weak interaction implies that the IRPD spectrum of PhCO~+-Ar is very close to the IR spectrum of bare PhCO~+. The detection of the C-H and C-O stretch fundamentals provides valuable information about the C-O and C-H bond strengths in this prototypical aromatic acylium ion. Moreover, a variety of weak combination and overtone bands are assigned. The global minimum on the PhCO~+-H2O potential has a planar charge-dipole configuration with D_0 = 41 kJ mol~(-1) (with only the two H2O protons being out-of-plane), in which the lone pairs of H2O interact with the positive partial charges on the carbonyl carbon atom and the proton of the CH group in ortho position/ The experimental IRPD spectra are in accord with the calculated global minima. The analysis of the charge distribution shows that the PhCO~+ cation is best represented as an oxocarbenium ion (Ph-C~+=O) with smaller contributions of the ketene structure (Ph~+=C=O). This view is supported by the geometrical and vibrational properties of PhCO~+ as well as the shape of the intermolecular PhCO~+-L dimer potentials.
机译：通过红外（IR）光谱，质谱和量子化学计算研究了具有Ar和H2O的闭壳苯甲酰基阳离子（C6H5CO〜+，PhCO〜+）的弱束缚簇，以表征闭壳的相互作用具有非极性和极性配体的芳族阳离子。 PhCO〜+ -L二聚体是通过在超音速等离子体膨胀中苯甲醛的电子电离而产生的。在C-O，C-H和O-H拉伸范围（2000-3900 cm〜（-1））下分析了PhCO〜+ -L（其中L = Ar和H2O）的红外光解离（IRPD）光谱。 PhCO〜+ -L二聚体的势能表面的特征是MP2 / 6-311 ++ G（2df，2pd），以定位各种最小值并确定其能量和振动特性。 PhCO〜+ -Ar与D_0 = 6 kJ mol〜（-1）的键合能更好地与芳环形成分子间π键。弱相互作用意味着PhCO〜+ -Ar的IRPD光谱非常接近裸PhCO〜+的IR光谱。 C-H和C-O拉伸基础的检测提供了有关此原型芳香族酰基离子中C-O和C-H键强度的有价值的信息。而且，分配了各种弱组合和泛音带。 PhCO〜+ -H2O势的全局最小值具有D_0 = 41 kJ mol〜（-1）的平面电荷偶极子构型（只有两个H2O质子在平面外），其中孤对H2O在邻位与羰基碳原子上的正部分电荷和CH基的质子相互作用/实验IRPD光谱与计算的整体最小值一致。电荷分布的分析表明，PhCO〜+阳离子最好地表示为氧碳鎓离子（Ph-C〜+ = O），而乙烯酮结构的贡献较小（Ph〜+ = C = O）。 PhCO〜+的几何和振动性质以及分子间PhCO〜+ -L二聚体势的形状为这一观点提供了支持。

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