Composite electron propagator methods for calculating ionization energies.
Accurate ionization energies of molecules may be determined efficiently with composite electron-propagator (CEP) techniques. These methods estimate the results of a calculation with an advanced correlation method and a large basis set by performing a series of more tractable calculations in which large basis sets are used with simpler approximations and small basis sets are paired with more demanding correlation techniques. The performance of several CEP methods, in which diagonal, second-order electron propagator results with large basis sets are combined with higher-order results obtained with smaller basis sets, has been tested for the ionization energies of closed-shell molecules from the G2 set. Useful compromises of accuracy and computational efficiency employ complete-basis-set extrapolation for second-order results and small basis sets in third-order, partial third-order, renormalized partial-third order, or outer valence Green's function calculations. Analysis of results for vertical as well as adiabatic ionization energies leads to specific recommendations on the best use of regular and composite methods. Results for 22 organic molecules of interest in the design of photovoltaic devices, benzo[a]pyrene, Mg-octaethylporphyrin, and C60 illustrate the capabilities of CEP methods for calculations on large molecules.
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849-5312, USA.
Manuel
M
Díaz-Tinoco
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849-5312, USA.
O
O
Dolgounitcheva
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849-5312, USA.
V G
VG
Zakrzewski
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849-5312, USA.
J V
JV
Ortiz