Dicyanogermylenes: A Tale
of Isomers and Interconversions
Ashwini Bundhun
Hassan
H. Abdallah
Ponnadurai Ramasami
Peter P. Gaspar
Henry
F. Schaefer
10.1021/ic301225w.s003
https://acs.figshare.com/articles/journal_contribution/Dicyanogermylenes_A_Tale_of_Isomers_and_Interconversions/2467618
A systematic investigation is carried out using the B3LYP,
BLYP,
and BHLYP functionals and MP2 level of theory to characterize the
low-lying electronic singlet and triplet GeC<sub>2</sub>N<sub>2</sub> isomers. The basis sets used are of double-ζ plus polarization
quality with additional s- and p-type diffuse functions, DZP++. Three
bent isomers Ge(CN)<sub>2</sub>, CNGeCN, and Ge(NC)<sub>2</sub> are
located on the singlet and triplet potential energy surfaces. In visualizing
the reaction pathways for the singlet isomerization of the bent isomers,
two three-membered [Ge, C, N] cyclic systems, with exocyclic −C–CN
and −C–NC bonding, appear on the energy surface.
Four types of electron affinities reported are: the adiabatic electron
affinity, the zero-point vibrationally corrected electron affinity,
the vertical electron affinity, and the vertical detachment energy
of the anion. The ionization energies and singlet–triplet gaps
for all isomers are also reported. The energetic ordering (kcal mol<sup>–1</sup>) (B3LYP) with zero-point vibrational energy corrections
for the singlet ground state isomers follows: Ge(CN)<sub>2</sub> (global
minimum) < CNGeCN (2.3) < Ge(NC)<sub>2</sub> (3.3) < Cyc_exo_CCN
(15.3) < Cyc_exo_CNC (30.6). All the bent and cyclic isomers are
found to be below the dissociation limit to Ge (<sup>3</sup>P) + C<sub>2</sub>N<sub>2</sub> (<sup>1</sup>Σ<sub>g</sub>). The rate
constants for all interconversions are evaluated using transition
state theory.
2012-11-19 00:00:00
MP 2 level
DZP
triplet GeC 2N isomers
electron affinity
BHLYP
transition state theory
singlet ground state isomers
adiabatic electron affinity
B 3LYP BLYP