title: Calculating Reaction Rates with Partial Hessians: Validation of the Mobile Block Hessian Approach.
abstract: In an earlier paper, the authors have developed a new method, the mobile block Hessian (MBH), to accurately calculate vibrational modes for partially optimized molecular structures [J. Chem. Phys. 2007, 126 (22), 224102]. The proposed procedure remedies the artifact of imaginary frequencies, occurring in standard frequency calculations, when parts of the molecular system are optimized at different levels of theory. Frequencies are an essential ingredient in predicting reaction rate coefficients due to their input in the vibrational partition functions. The question arises whether the MBH method is able to describe the chemical reaction kinetics in an accurate way in large molecular systems where a full quantum chemical treatment at a reasonably high level of theory is unfeasible due to computational constraints. In this work, such a validation is tested in depth. The MBH method opens a lot of perspectives in predicting accurate kinetic parameters in chemical reactions where the standard full Hessian procedure fails.
authors.affiliation: Center for Molecular Modeling, Ghent University, Proeftuinstraat 86, B-9000 Gent, Belgium.
authors.forename: A
authors.initials: A
authors.lastname: Ghysels
authors.affiliation: Center for Molecular Modeling, Ghent University, Proeftuinstraat 86, B-9000 Gent, Belgium.
authors.forename: V
authors.initials: V
authors.lastname: Van Speybroeck
authors.affiliation: Center for Molecular Modeling, Ghent University, Proeftuinstraat 86, B-9000 Gent, Belgium.
authors.forename: T
authors.initials: T
authors.lastname: Verstraelen
authors.affiliation: Center for Molecular Modeling, Ghent University, Proeftuinstraat 86, B-9000 Gent, Belgium.
authors.forename: D
authors.initials: D
authors.lastname: Van Neck
authors.affiliation: Center for Molecular Modeling, Ghent University, Proeftuinstraat 86, B-9000 Gent, Belgium.
authors.forename: M
authors.initials: M
authors.lastname: Waroquier