Gas-phase
infrared photodissociation spectra of [V(CO2)
n
]+ complexes revealed three
new vibrational bands at 1140, 1800, and 3008 cm–1 at n = 7, the features of which are retained in
the larger clusters (Ricks, A. M.; Brathwaite, A. D.; Duncan, M. A. J. Phys. Chem. A
2013,
117, 11490–11498). However, structural assignment of this intriguing
feature remains open. Herein, quantum chemical calculations on [V(CO2)7]+ were carried out to identify the
structure of the low-lying isomers and to assign the observed spectral
features. The comparison of calculated infrared spectra of [V(CO2)7]+ with experimental infrared spectra
identified the formation of a bent CO2
– species, suggesting the ligand-induced activation of CO2 by the vanadium cation. The structures and infrared spectra of [Cr(CO2)7]+ and [Mn(CO2)7]+ were also predicted and discussed.
Infrared spectra of the neutral dimethylamine−methanol cluster, DMA− CH 3 OH, were measured in the spectral range of 2800−3900 cm −1 using an infraredvacuum ultraviolet (IR-VUV) scheme. Quantum chemical calculations and ab initio molecular dynamic (AIMD) simulations were carried out to understand the experimental spectral features. Experimental and theoretical results reveal the coexistence of N•••HO and O•••HN hydrogen-bonded structures. AIMD simulations show that the methyl group in methanol internally rotates around the N•••O axis, addressing the dynamic effect of the fluctuation of hydrogen bonds on the vibrational features. The bonding analysis was performed to elucidate the nature of the intermolecular interaction between DMA and CH 3 OH. The present work provides the fundamental understanding of hydrogen-bonding networks in the amine−alcohol complexes.
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