and as discussed in Section 11.2.3 the user has the option to choose either the original value suggested by Klamt,Klamt:1993, Klamt:1996 , or else as in, e.g., Refs. Truong:1995, Cossi:2003, Lange:2011b. More importantly, however, COSMO differs from C-PCM in that the former includes a correction for outlying charge that goes beyond Eq. (11.12), whereas C-PCM consists of nothing more than induced surface charges computed (self-consistently) according to Eq. (11.12)
Upon solution of Eq. (11.12), the outlying charge correction in COSMOKlamt:1996, Baldridge:1997 is obtained by first defining a larger cavity that is likely to contain essentially all of the solute’s electron density; in practice, this typically means using atomic radii of 1.95 , where denotes the original atomic van der Waals radius that was used to compute . (Note that unlike the PCMs described in Sections 11.2.2 and 11.2.3, where the atomic radii have default values but a high degree of user-controllability is allowed, the COSMO atomic radii are parameterized for this model and are fixed.) A new set of charges, , is then computed on this larger cavity surface, and the charges on the original cavity surface are adjusted to new values, . Finally, a corrected electrostatic potential on the original surface is computed according to . It is this potential that is used to compute the solute–continuum electrostatic interaction (polarization energy), . (For comparison, when the C-PCM approach described in Section 11.2.2 is used, the electrostatic polarization energy is , computed using the original surface charges and surface electrostatic potential .) With this outlying charge correction, Q-Chem’s implementation of COSMO resembles the one in Turbomole.Schafer:2000
A COSMO calculation is requested by setting SOLVENT_METHOD = COSMO in the $rem section, in addition to normal job control variables. The keyword Dielectric in the $solvent section is used to set the solvent’s static dielectric constant, as described above for other solvation models. COSMO calculations can also be used as a starting point for COSMO-RS calculations,Klamt:2001, Klamt:2010 where “RS” stands for “real solvent”. The COSMO-RS approach is not included in Q-Chem and requires the COSMOtherm program, which is licensed separately through COSMOlogic.COSMOlogic Q-Chem users who are interested in COSMOtherm can request special versions of Q-Chem for the generation of -surface files that are needed by COSMOtherm.