J. A.

Tossell
H2CO3(s): A new candidate for CO2 capture and sequestration
2 pages
1 Figure
Computational Methods:

For the calculation of gas-phase free energies we use when possible

the CBS-QB3 method (33), a “composite” quantum chemical method which
determines equilibrium geometries at essentially the 6-311G(d,p) B3LYP
level (although using the slightly modified CBSB7 basis set to improve the
treatment of correlation) and uses as its highest level single point correlated
calculation a CCSD(T) calculation at the equilibrium geometry with a 6-
31+G(d,p) basis. Unfortunately the computer time required for the highly
demanding CCSD(T) step (34) in this method scales as about the seventh
power of the number of electrons, so the method becomes extremely
demanding for the larger oligomeric species. We have thus applied it to the
monomeric and dimeric species only. The substantially less demanding
CBS-Lq method (35) has also been employed (which uses smaller basis sets
for the correlated steps and 3-21G* HF for the geometry optimization,
among other differences), even though this method is expected to give both
less accurate geometries and less accurate energies than CBS-QB3. Of
course, the advantage is that this method can be applied to oligomers
(H2CO3)n with n ≤ 4. This allows us to more clearly elucidate trends in H-
bonding energies and to probe the effects of interactions other than H-
bonding which could be important in the stabilization of pairs and multiples
of H-bonded chains of oligomers.
Vibrational spectra for the H2CO3 species have been obtained at
several levels of approximation. First, we use the harmonic vibrational
frequencies obtained at the CBSB7 B3LYP level during the CBS-QB3
calculation. We then calculated harmonic vibrational frequencies at the 6-
311+G(2d,p) CCSD level if computationally feasible, which restricts us to
the monomeric species. Anharmonic frequencies were then calculated at the
CBSB7 B3LYP level using the second-order perturbation theory approach
(36) implemented in GAUSSIAN03, for the monomeric and dimeric species.
Such a boot-strapping approach has been used with success by others (37,
38). To evaluate the hydration free energies we use the conductor
polarizable continuum method, or CPCM, version (39) of the polarizable
continuum method (40).
We have also calculated NMR shieldings for a number of the species
considered, to establish additional criteria for their identification, using the
GIAO version of coupled Hartree-Fock perturbation theory (41). We have
utilized 6-311+G(2d,p) basis sets and HF, MP2 and B3LYP versions of the
GIAO method. S1
 UV/visible absorption energies and intensities were also calculated
using a 6-311+G(2d,p) basis and the TD B3LYP method (42) to establish
whether the species considered were photolytically stable within the Earth’s
atmosphere.
All calculations were done using GAUSSIAN03 (43) and structures
were visualized using GAUSSVIEW (44).

S2
(H2CO3)2
 (H2CO3)3

(H2CO3)4 chain

(H2CO3)4
dimer of dimers
 (H2CO3)2 transition state

Fig. S1