Shayesteh Alireza, Henderson Robert D E, Le Roy Robert J, Bernath Peter F
Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1.
J Phys Chem A. 2007 Dec 13;111(49):12495-505. doi: 10.1021/jp075704a. Epub 2007 Nov 20.
New high-resolution visible emission spectra of the MgH molecule have been recorded with high signal-to-noise ratios using a Fourier transform spectrometer. Many bands of the A 2Pi-->X 2Sigma+ and B' 2Sigma+-->X 2Sigma+ electronic transitions of 24MgH were analyzed; the new data span the v' = 0-3 levels of the A 2Pi and B'2Sigma+ excited states and the v''=0-11 levels of the X 2Sigma+ ground electronic state. The vibration-rotation energy levels of the perturbed A 2Pi and B' 2Sigma+ states were fitted as individual term values, while those of the X 2Sigma+ ground state were fitted using the direct-potential-fit approach. A new analytic potential energy function that imposes the theoretically correct attractive potential at long-range, and a radial Hamiltonian that includes the spin-rotation interaction were employed, and a significantly improved value for the ground state dissociation energy of MgH was obtained. The v''=11 level of the X 2Sigma+ ground electronic state was found to be the highest bound vibrational level of 24MgH, lying only about 13 cm(-1) below the dissociation asymptote. The equilibrium dissociation energy for the X 2Sigma+ ground state of 24MgH has been determined to be De=11104.7+/-0.5 cm(-1) (1.37681+/-0.00006 eV), whereas the zero-point energy (v''=0) is 739.11+/-0.01 cm(-1). The zero-point dissociation energy is therefore D0=10365.6+/-0.5 cm(-1) (1.28517+/-0.00006 eV). The uncertainty in the new experimental dissociation energy of MgH is more than 2 orders of magnitude smaller than that for the best value available in the literature. MgH is now the only hydride molecule other than H2 itself for which all bound vibrational levels of the ground electronic state are observed experimentally and for which the dissociation energy is determined with subwavenumber accuracy.
利用傅里叶变换光谱仪记录了MgH分子新的高分辨率可见发射光谱,其信噪比很高。分析了24MgH的A 2Pi→X 2Sigma+和B' 2Sigma+→X 2Sigma+电子跃迁的许多谱带;新数据涵盖了A 2Pi和B'2Sigma+激发态的v' = 0 - 3能级以及X 2Sigma+基电子态的v'' = 0 - 11能级。对受扰动的A 2Pi和B' 2Sigma+态的振转能级拟合为单个项值,而对X 2Sigma+基态的能级则采用直接势拟合方法。采用了一种新的解析势能函数,该函数在长程施加理论上正确的吸引势,以及一个包含自旋 - 转动相互作用的径向哈密顿量,得到了MgH基态离解能的显著改进值。发现X 2Sigma+基电子态的v'' = 11能级是24MgH的最高束缚振动态能级,仅比离解渐近线低约13 cm(-1)。已确定24MgH的X 2Sigma+基态的平衡离解能为De = 11104.7±0.5 cm(-1) (1.37681±0.00006 eV),而零点能(v'' = 0)为739.11±0.01 cm(-1)。因此,零点离解能为D0 = 10365.6±0.5 cm(-1) (1.28517±0.00006 eV)。MgH新实验离解能的不确定度比文献中最佳值的不确定度小两个多数量级。MgH现在是除H2本身之外唯一一种其基电子态的所有束缚振动态能级都通过实验观测到且离解能以亚波数精度确定的氢化物分子。