Wang Qiang, Ding Yi-Hong, Xie Hong-Bin, Sun Chia-Chung
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
J Comput Chem. 2006 Mar;27(4):505-14. doi: 10.1002/jcc.20364.
Theoretical investigations are performed for the first time on the simplest hydrogenated germanium cyanide [H,Ge,C,N], whose analogs [H,C(2),N] and [H,Si,C,N] have been detected in space and laboratory, respectively. The detailed potential energy surfaces in both singlet and triplet states are constructed at the CCSD(T)/6-311+G(3df,2p)//B3LYP/6-31G(d)+ZPVE level, including 18 minimum isomers and 26 interconversion transition states. The former three low-lying and kinetically stabilized isomers are HGeCN (1)1 (0.0 kcal/mol), HGeNC (1)2 (5.1 kcal/mol), and cyclic cCHNGe(1)7 (11.1 kcal/mol). In addition, five isomers HCNGe (1)3 (33.8), HNCGe (1)5 (29.8), cNHCGe (1)8 (37.9), HGeCN (3)1 (30.1), and HNCGe (3)5 (26.5) each have considerable barriers, despite their high energies. Future laboratory characterization and astrophysical detection of the eight [H,Ge,C,N] isomers, especially the former three low-lying species (1)1, (1)2, and (1)7, are highly recommended. The accurate spectroscopic data at the QCISD/6-311G(d,p) level are provided. For some species, the CBS-QB3 calculations are also performed. Wherever possible, comparisons with the analogous [H,C(2),N] and [H,Si,C,N] are made on the structural, energetic, and bonding properties.
首次对最简单的氢化锗氰化物[H,Ge,C,N]进行了理论研究,其类似物[H,C(2),N]和[H,Si,C,N]已分别在太空和实验室中被检测到。在CCSD(T)/6 - 311 + G(3df,2p)//B3LYP/6 - 31G(d)+ZPVE水平构建了单重态和三重态的详细势能面,包括18个最低异构体和26个相互转化的过渡态。前三个能量较低且动力学稳定的异构体是HGeCN (1)1(0.0千卡/摩尔)、HGeNC (1)2(5.1千卡/摩尔)和环状cCHNGe(1)7(11.1千卡/摩尔)。此外,五个异构体HCNGe (1)3(33.8)、HNCGe (1)5(29.8)、cNHCGe (1)8(37.9)、HGeCN (3)1(30.1)和HNCGe (3)5(26.5)尽管能量较高,但各自都有相当大的能垒。强烈建议未来在实验室中对这八种[H,Ge,C,N]异构体进行表征,并在天体物理学中进行检测,尤其是前三个能量较低的物种(1)1、(1)2和(1)7。提供了QCISD/6 - 311G(d,p)水平的精确光谱数据。对于一些物种,还进行了CBS - QB3计算。在可能的情况下,对类似的[H,C(2),N]和[H,Si,C,N]的结构、能量和键合性质进行了比较。