二氯硅烷：从头算非谐力场、偶极矩和红外振动跃迁

SiH2Cl2: ab initio anharmonic force field, dipole moments, and infrared vibrational transitions.

作者信息

Liu An-Wen, Hu Shui-Ming, Zhu Qing-Shi

机构信息

Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, China.

出版信息

J Chem Phys. 2005 Nov 1;123(17):174305. doi: 10.1063/1.2090267.

DOI:10.1063/1.2090267

PMID:16375526

Abstract

The vibrational spectra of SiH2Cl2 have been recorded in the 1000-13,000 cm(-1) region, utilizing the Fourier-transform spectroscopy and Fourier-transform intracavity laser absorption spectroscopy. Totally 61 band centers and intensities are derived from the infrared spectra. An ab initio quartic force field is obtained by applying the second-order Moller-Plesset perturbation theory and correlation-consistent polarized valence triplet-zeta basis sets [J. Chem. Phys. 90, 1007 (1989); 98, 1358 (1993)]. Most observed bands are assigned by the vibration analysis based on the second-order perturbation theory. Reduced-dimensional ab initio dipole moment functions (two dimensional and three dimensional) have also been calculated to investigate the absolute band intensities of the SiH2 chromophore. The calculated values agree reasonably with the observed ones.

摘要

利用傅里叶变换光谱法和傅里叶变换腔内激光吸收光谱法，在1000 - 13000 cm⁻¹区域记录了SiH₂Cl₂的振动光谱。从红外光谱中总共得到了61个谱带中心和强度。通过应用二阶莫勒 - 普列斯特定理微扰理论和相关一致极化价三重ζ基组得到了一个从头算四次力场[《化学物理杂志》90, 1007 (1989); 98, 1358 (1993)]。基于二阶微扰理论的振动分析对大多数观测到的谱带进行了归属。还计算了降维从头算偶极矩函数（二维和三维），以研究SiH₂发色团的绝对谱带强度。计算值与观测值相当吻合。