title: Analytic second derivatives of the energy in the fragment molecular orbital method.
abstract: We developed the analytic second derivatives of the energy for the fragment molecular orbital (FMO) method. First we derived the analytic expressions and then introduced some approximations related to the first and second order coupled perturbed Hartree-Fock equations. We developed a parallel program for the FMO Hessian with approximations in GAMESS and used it to calculate infrared (IR) spectra and Gibbs free energies and to locate the transition states in SN2 reactions. The accuracy of the Hessian is demonstrated in comparison to ab initio results for polypeptides and a water cluster. By using the two residues per fragment division, we achieved the accuracy of 3 cm(-1) in the reduced mean square deviation of vibrational frequencies from ab initio for all three polyalanine isomers, while the zero point energy had the error not exceeding 0.3 kcal/mol. The role of the secondary structure on IR spectra, zero point energies, and Gibbs free energies is discussed.
authors: Department of Biomolecular Engineering, Tokyo Institute of Technology, Yokohama, Kanagawa, Japan. nakata.h.ab@m.titech.ac.jp
authors: Hiroya
authors: H
authors: Nakata
authors: Takeshi
authors: T
authors: Nagata
authors: Dmitri G
authors: DG
authors: Fedorov
authors: Satoshi
authors: S
authors: Yokojima
authors: Kazuo
authors: K
authors: Kitaura
authors: Shinichiro
authors: S
authors: Nakamura
mesh_terms: D007700:Kinetics; D009010:Monte Carlo Method; D011789:Quantum Theory