This presentation has been moved. To view this presentation, please visit http://pubs.acs.org/iapps/liveslides/pages/index.htm?mscNo=jz300859t [CTi72+]: Heptacoordinate Carbon Motif?

1. [CTi72+]: Heptacoordinate
Carbon Motif?
Yi Gao,1,2* Nan Shao, Rulong Zhou,
Guiling Zhang, Xiao Cheng Zeng2*
1Shanghai Institute of Applied Physics, Chinese
Academy of Sciences, Shanghai, China
2University of Nebraska-Lincoln, Lincoln, NE
68588 USA
J. Phys. Chem. Lett. 2012, 3, 2264 -2268 1

2. Motivation-Hypercoordinated Carbon
Experiment
CH5+ Five-Coordinated Six-Coordinated
(White et al. Science, 1999, 284, 135) (Yamaguchi et al. JACS, 2008, 130, 6894)
Theory
CH4 in Nature
Four-Coordinated Not the Global-Minimum!
(Averkiev et al. JACS,
2008, 130, 9248)
(Wang and Schleyer, Science, 2001, 292, 2465)
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3. Theoretical Methodology
1. Combine basin-hopping global-minimum search and DFT to locate
low-energy candidates of [CTi72+] and [CTi72+][BH4-]2.
2. Five density functionals PBE, ωB97xD, B3LYP, M06, TPSSh are
used to optimize the geometries and analyze the vibrational
frequencies. And CCSD single-point calculations are carried out to
evaluate the their relative stabilities.
3. PBE/SDD/6-311+G(d) is used to optimize [CTi7][C16H9]2 and further
build quasi-1D nanowire [CTi7]n[C16H9]n.
4. Ab initio molecular dynamics is applied to examine the thermal
stability of finite quasi-1D nanowire [CTi7]2[C16H9]3H2 at 400K for 5
ps.
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4. Relative Stability of the isomers for
[CTi72+] and [CTi72+][BH4-]2
ω
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5. Quasi-1D Nanowire: [CTi7]n[C16H9]n
Metallic!
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6. Ab initio MD of [CTi7]2[C16H9]3H2 at 400 K
0 ps 1.5 ps
3.0 ps 5.0 ps
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7. Conclusions
A highly stable heptacoordinate carbon
motif [CTi72+] is predicted theoretically. It
could bind with two anion groups to form
a stable netural molecule and could also
be used to build quasi-1D nanowire. Its
existence is waiting for futher
experimental confirmation.
Acknowledgments
Shanghai Institute of Applied Physics,
CAS (Y290011011)
NSF (EPS-1010674)
ARL (W911NF1020099)
Supercomputing Center of CAS in Beijing
UNL-Holland Computing Center
Yi Gao Xiao Cheng Zeng
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