Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA.
J Phys Chem A. 2013 Feb 14;117(6):1001-10. doi: 10.1021/jp301679m. Epub 2012 Apr 19.
The vibrational spectra of vanadium carbonyl cations of the form V(CO)(n)(+), where n = 1-7, were obtained via mass-selected infrared laser photodissociation spectroscopy in the carbonyl stretching region. The cations and their argon and neon "tagged" analogues were produced in a molecular beam via laser vaporization in a pulsed nozzle source. The relative intensities and frequency positions of the infrared bands observed provide distinctive patterns from which information on the coordination and spin states of these complexes can be obtained. Density functional theory is carried out in support of the experimental spectra. Infrared spectra obtained by experiment and predicted by theory provide evidence for a reduction in spin state as the ligand coordination number increases. The octahedral V(CO)(6)(+) complex is the fully coordinated experimental species. A single band at 2097 cm(-1) was observed for this complex red-shifted from the free CO vibration at 2143 cm(-1).
通过在羰基伸缩区域进行质量选择的红外激光光解光谱学，获得了形式为 V(CO)(n)(+)的钒羰基阳离子的振动光谱，其中 n = 1-7。阳离子及其氩和氖“标记”类似物通过激光蒸发在脉冲喷嘴源中在分子束中产生。观察到的红外带的相对强度和频率位置提供了独特的模式，从中可以获得有关这些配合物的配位和自旋状态的信息。密度泛函理论用于支持实验光谱。通过实验获得的红外光谱和理论预测提供了证据，表明随着配体配位数的增加，自旋态降低。八面体 V(CO)(6)(+)配合物是完全配位的实验物种。该配合物的 2097 cm(-1)处的单个带从游离 CO 振动的 2143 cm(-1)处红移。
