ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, UK.
School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, UK.
Phys Chem Chem Phys. 2019 Dec 7;21(45):24950-24955. doi: 10.1039/c9cp05191k. Epub 2019 Nov 8.
The solid state vibrational spectra of M(CO), (M = Cr, Mo, W) in the region below 800 cm have been assigned by a combination of infrared, Raman and the first reported inelastic neutron scattering (INS) spectra from homoleptic metal carbonyls. This region comprises of the lattice modes, the OC-M-CO deformations, the M-C[triple bond, length as m-dash]O bends and the M-C stretches. Three modes that are forbidden in both the infrared and Raman spectra of the parent O symmetry gas phase molecule occur in this region. The absence of selection rules for INS spectroscopy means that all three modes are clearly seen for the first time, all previous work has relied on overtone and combination modes. Periodic density functional theory calculations of the complete orthorhombic structure support the assignments.
M(CO)（M = Cr、Mo、W）在低于 800cm 的固态振动光谱已通过组合红外、拉曼和首次报道的同核金属羰基的非弹性中子散射（INS）光谱进行了分配。该区域包括晶格模式、OC-M-CO 变形、M-C[三重键，长度为 m-dash]O 弯曲和 M-C 伸展。在母体 O 对称气相分子的红外和拉曼光谱中都禁止的三个模式出现在该区域。INS 光谱学没有选择规则意味着首次清楚地看到了所有三个模式，所有以前的工作都依赖于泛频和组合模式。完整正交结构的周期性密度泛函理论计算支持分配。
