Atomization energies of the carbon clusters Cn (n=2--10) revisited by means of W4 theory as well as density functional, Gn, and CBS methods

Details Atomization energies of the carbon clusters Cn (n=2--10) revisited by means of W4 theory as well as density functional, Gn, and CBS methods Atomization energies of the carbon clusters Cn (n=2--10) revisited by means of W4 theory as well as density functional, Gn, and CBS methods

2008-12-19

arxiv.org/abs/0812.3852v1

Molecular Physics 107, 977-990 (2009)

Physics

Chemical Physics

[Mol. Phys., in press (Henry F. Schaefer III Festschrift)]

Scientific paper

10.1080/00268970802708959

The thermochemistry of the carbon clusters C$_n$ (n=2--10) has been revisited by means of W4 theory and W3.2lite theory. Particularly the larger clusters exhibit very pronounced post-CCSD(T) correlation effects. Despite this, our best calculated total atomization energies agree surprisingly well with 1991 estimates obtained from scaled CCD(ST)/6-31G* data. Accurately reproducing the small singlet-triplet splitting in C$_2$ requires inclusion of connected quintuple and sextuple excitations. Post-CCSD(T) correlation effects in C$_4$ stabilize the linear form. Linear/cyclic equilibria in C$_6$, C$_8$, and C$_{10}$ are not strongly affected by connected quadruples, but they are affected by higher-order triples, which favor polyacetylenic rings but disfavor cumulenic ones. Near the CCSD(T) basis set limit, C$_{10}$ does undergo bond angle alternation in the bottom-of-the-well structure, although it is expected to be absent in the vibrationally averaged structure. The thermochemistry of these systems, and particularly the longer linear chains, is a particularly difficult test for density functional methods. Particularly for the smaller chains and the rings, double-hybrid functionals clearly outperform convential DFT functionals for these systems. Among compound thermochemistry schemes, G4 clearly outperforms the other members of the G$n$ family. Our best estimates for total atomization energies at 0 K should be reliable to 1 kJ/mol up to C$_5$ inclusive, and to better than 1 kcal/mol up to C$_9$ inclusive.

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