TY - CHAP

T1 - A Quantum Chemical Approach to Free Energy Calculation for Chemical Reactions in Condensed System

T2 - Combination of a Quantum Chemical Method with a Theory of Statistical Mechanics

AU - Takahashi, Hideaki

AU - Matubayasi, Nobuyuki

AU - Nakano, Masayoshi

PY - 2008/1/1

Y1 - 2008/1/1

N2 - A recent development to compute free energy changes associated with chemical processes in condensed phase has been reviewed. The methodology is based on the hybrid quantum mechanical/molecular mechanical (QM/MM) approach combined with the novel theory of solutions, where the electronic structure calculation in the QM subsystem is conducted by the Kohn–Sham density functional theory (KS-DFT) utilizing the real-space grids to represent the one-electron orbitals, while the distribution functions for MM molecules needed to compute the free energy change of interest are constructed in terms of the QM/MM interaction energies. The following sections are devoted to the overview of the existing methodologies for the free energy calculation for chemical event and to the detailed description of the real-space-based DFT as well as the theory of solutions. Next we present a theory to combine the quantum mechanics with the statistical mechanics, where an emphasis will be placed on the treatment of the many-body interaction inherent with the quantum mechanical object. Finally, the several applications of the methodology to the solution system are presented to demonstrate the accuracy and efficiency of the method.

AB - A recent development to compute free energy changes associated with chemical processes in condensed phase has been reviewed. The methodology is based on the hybrid quantum mechanical/molecular mechanical (QM/MM) approach combined with the novel theory of solutions, where the electronic structure calculation in the QM subsystem is conducted by the Kohn–Sham density functional theory (KS-DFT) utilizing the real-space grids to represent the one-electron orbitals, while the distribution functions for MM molecules needed to compute the free energy change of interest are constructed in terms of the QM/MM interaction energies. The following sections are devoted to the overview of the existing methodologies for the free energy calculation for chemical event and to the detailed description of the real-space-based DFT as well as the theory of solutions. Next we present a theory to combine the quantum mechanics with the statistical mechanics, where an emphasis will be placed on the treatment of the many-body interaction inherent with the quantum mechanical object. Finally, the several applications of the methodology to the solution system are presented to demonstrate the accuracy and efficiency of the method.

KW - Energy representation

KW - Free energy change

KW - Radial distribution function

KW - Solvation free energy

KW - Solvent interaction

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U2 - 10.1007/978-1-4020-8270-2_17

DO - 10.1007/978-1-4020-8270-2_17

M3 - Chapter

AN - SCOPUS:84988334172

T3 - Challenges and Advances in Computational Chemistry and Physics

SP - 455

EP - 505

BT - Challenges and Advances in Computational Chemistry and Physics

PB - Springer

ER -