Chattopadhyaya Surya, Pramanik Anup, Banerjee Amartya, Das Kalyan Kumar
Department of Chemistry, Physical Chemistry Section, Jadavpur University, Kolkata 700 032, India.
J Phys Chem A. 2006 Nov 9;110(44):12303-11. doi: 10.1021/jp062610c.
Ab initio based configuration interaction calculations have been carried out to study the low-lying electronic states and spectroscopic properties of the heaviest nonradioactive silicon chalcogenide molecule and its monopositive ion. Spectroscopic constants and potential energy curves of states of both SiTe and SiTe+ within 5 eV are reported. The calculated dissociation energies of SiTe and SiTe+ are 4.41 and 3.52 eV, respectively. Effects of the spin-orbit coupling on the electronic spectrum of both the species are studied in detail. The spin-orbit splitting between the two components of the ground state of SiTe+ is estimated to be 1880 cm(-1). Transitions such as 0+ (II)-X1Sigma(+)0+, 0+ (III)-X1Sigma(+)0+, E1Sigma(+)0+ -X1Sigma(+)0+, and A1Pi1-X1Sigma(+)0+ are predicted to be strong in SiTe. The radiative lifetime of the A1Pi state is less than a microsecond. The X(2)2Pi(1/2)-X(1)2Pi(3/2) transition in SiTe+ is allowed due to spin-orbit mixing. However, it is weak in intensity with a partial lifetime for the X2 state of about 108 ms. The electric dipole moments of both SiTe and SiTe+ in their low-lying states are calculated. The vertical ionization energies for the ionization of the ground-state SiTe to different ionic states are also reported.
基于从头算的组态相互作用计算已被用于研究最重的非放射性硅硫属化物分子及其单正离子的低电子态和光谱性质。报告了SiTe和SiTe⁺在5 eV范围内的光谱常数和态的势能曲线。计算得到SiTe和SiTe⁺的离解能分别为4.41和3.52 eV。详细研究了自旋轨道耦合对这两种物质电子光谱的影响。SiTe⁺基态两个分量之间的自旋轨道分裂估计为1880 cm⁻¹。预计SiTe中诸如0⁺(II)-X¹Σ⁺0⁺、0⁺(III)-X¹Σ⁺0⁺、E¹Σ⁺0⁺ -X¹Σ⁺0⁺和A¹Π¹-X¹Σ⁺0⁺等跃迁是强跃迁。A¹Π态的辐射寿命小于1微秒。由于自旋轨道混合，SiTe⁺中的X(²)²Π(¹/₂)-X(¹)²Π(³/₂)跃迁是允许的。然而，其强度较弱，X²态的部分寿命约为108毫秒。计算了SiTe和SiTe⁺在其低能态的电偶极矩。还报告了基态SiTe电离到不同离子态的垂直电离能。
