Larkin Joseph D, Schaefer Henry F
Center for Computational Chemistry, University of Georgia, Athens, Georgia 30602, USA.
J Chem Phys. 2004 Nov 15;121(19):9361-7. doi: 10.1063/1.1790951.
Recently, Ishida and co-workers have isolated silylene radical anions via the one-electron reduction of isolable cyclic dialkylsilylenes, discovering these corresponding radical anions to be relatively stable at low temperatures. Herein we report theoretical predictions of the adiabatic electron affinities (AEA), vertical electron affinities, and vertical detachment energies of a series of methyl, silyl, and halosubstituted silylene compounds. This research utilizes the carefully calibrated DZP++ basis with the combination of the popular nonhybrid and hybrid DFT functionals, BLYP, B3LYP, and BHHLYP. The level of theory employed and the ensemble of species under study confirm the ability of silylenes to bind excess electrons with Si(SiH(3))(2) being the most effective, having a predicted AEA of 1.95 eV. While it is known that methyl substituents have a diminishing effect on the computed electron affinities (EAs), it is shown that fluorine shows an analogous negative effect. Similarly, previous suggestions that Si(CH(3))(2) will not bind an electron appear incorrect, with EA[Si(CH(3))(2)] predicted here to be 0.46 eV.
最近，石田及其同事通过可分离的环状二烷基硅烯的单电子还原分离出了硅烯自由基阴离子，发现这些相应的自由基阴离子在低温下相对稳定。在此，我们报告了一系列甲基、硅基和卤代硅烯化合物的绝热电子亲和能（AEA）、垂直电子亲和能和垂直脱附能的理论预测。本研究使用了经过仔细校准的DZP++基组，并结合了流行的非杂化和杂化密度泛函理论（DFT）泛函BLYP、B3LYP和BHHLYP。所采用的理论水平和所研究的物种集合证实了硅烯结合多余电子的能力，其中Si(SiH(3))(2)最为有效，预测的AEA为1.95 eV。虽然已知甲基取代基对计算出的电子亲和能（EA）有减弱作用，但研究表明氟也有类似的负效应。同样，之前认为Si(CH(3))(2)不会结合电子的观点似乎是错误的，此处预测EA[Si(CH(3))(2)]为0.46 eV。
