Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
}
TY - JOUR
T1 - Influence of Coulomb-attenuation on exchange-correlation functional quality
AU - Peach, Michael J. G.
AU - Cohen, Aron J.
AU - Tozer, David J.
PY - 2006
Y1 - 2006
N2 - The dependence of functional quality on the attenuation parameters-which control the limiting (r(12) -> 0, infinity) values and the rate of attenuation-is investigated for a Coulomb-attenuated exchange-correlation functional. For the attenuation and functional form considered, satisfaction of an exact long-range condition is detrimental for properties such as atomisation energies and bond lengths, but does improve classical reaction barriers and small molecule electronic excitation energies. The functionals considered can provide high quality valence, Rydberg, intramolecular and asymptotic intermolecular charge transfer (CT) excitations, but none are able to provide a simultaneously optimal description of all classes; CT excitations are not necessarily improved compared to those from conventional functionals. The study highlights the need for further development of Coulomb-attenuated functionals.
AB - The dependence of functional quality on the attenuation parameters-which control the limiting (r(12) -> 0, infinity) values and the rate of attenuation-is investigated for a Coulomb-attenuated exchange-correlation functional. For the attenuation and functional form considered, satisfaction of an exact long-range condition is detrimental for properties such as atomisation energies and bond lengths, but does improve classical reaction barriers and small molecule electronic excitation energies. The functionals considered can provide high quality valence, Rydberg, intramolecular and asymptotic intermolecular charge transfer (CT) excitations, but none are able to provide a simultaneously optimal description of all classes; CT excitations are not necessarily improved compared to those from conventional functionals. The study highlights the need for further development of Coulomb-attenuated functionals.
KW - BASIS-SETS
KW - RANGE
KW - DER-WAALS INTERACTIONS
KW - ORGANIC-COMPOUNDS
KW - KOHN-SHAM ORBITALS
KW - TRANSFER EXCITED-STATES
KW - AMINOBENZONITRILES
KW - DENSITY FUNCTIONALS
KW - CHARGE-TRANSFER EXCITATIONS
KW - CORRELATION-ENERGY
U2 - 10.1039/b608553a
DO - 10.1039/b608553a
M3 - Journal article
VL - 8
SP - 4543
EP - 4549
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 39
ER -