Novel computational chemistry approaches for studying physico-chemical properties of zeolite materials Akira Miyamoto a,b, * , Yasunori Kobayashi b , Mohamed Elanany b , Hideyuki Tsuboi b , Michihisa Koyama b , Akira Endou b , Hiromitsu Takaba b , Momoji Kubo b,c , Carlos A. Del Carpio b , Parasuraman Selvam a,d a New Industry Creation Hatchery Center (NICHe), Tohoku University, 6-6-10 Aoba, Aramaki, Aoba-ku, Sendai 980-8579, Japan b Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, 6-6-11-1302 Aoba, Aramaki, Aoba-ku, Sendai 980-8579, Japan c PRESTO, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan d Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India Received 12 August 2006; received in revised form 26 November 2006; accepted 6 December 2006 Available online 21 December 2006 Abstract Computational chemistry has made tremendous impact on the development of zeolite materials. Molecular dynamics (MD), Monte Carlo (MC), quantum chemistry (QC), and quantum chemical molecular dynamics (QCMD) methods have been applied to the studies of diffusion processes, adsorption characteristics, catalytic reaction mechanism, synthesis processes, acidic properties, etc. in zeolite mate- rials. However, these traditional approaches are not able to accommodate complicated realistic systems because of their approximations and of the limitation of calculation models. To establish a novel computational chemistry approach for exploring new physico-chemical properties of zeolite materials, we have developed a novel dual ensemble MD (DEMD) program and original tight-binding QCMD pro- gram, ‘Colors’. The DEMD program can perform the permeation and separation dynamics simulation considering the gradient of chem- ical potential in a simulation cell. Colors program is over 5000 times faster than the traditional first-principles QCMD simulator. Hence, it enables us to employ more realistic large-scale models. Furthermore, we have also performed large-scale QC calculations based on the density functional theory (DFT) with a whole unit cell model of a zeolite material considering the periodic boundary condition (PBC). In this review, we put forward the application of our novel theoretical approaches for studying physico-chemical properties of zeolite materials. Ó 2007 Elsevier Inc. All rights reserved. Keywords: Dual ensemble molecular dynamics method; Tight-binding quantum chemical molecular dynamics method; Density functional theory calc- ulation with periodic boundary conditions 1. Introduction In recent years, computational chemistry has made bril- liant progress and substantial impact on the development of a variety of engineering materials including zeolite. Studies at electronic and atomic level are expected to play a critical role in predicting new zeolite materials with unu- sual characteristics. Since experimental information obtained in atomic level is exiguous, computational chem- istry approach is particularly fascinating. This approach is hoped to contribute not only the prediction of physico- chemical properties of zeolite materials but also the design of novel zeolite materials, with the help of significant pro- gress in the theory and computation power. Computational chemistry methods such as molecular dynamics (MD), Monte Carlo (MC), and quantum chem- istry (QC) methods have been employed for the theoretical 1387-1811/$ - see front matter Ó 2007 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2006.12.025 * Corresponding author. Address: New Industry Creation Hatchery Center (NICHe), Tohoku University, 6-6-10 Aoba, Aramaki, Aoba-ku, Sendai 980-8579, Japan. Tel.: +81 22 795 7233; fax: +81 22 795 7235. E-mail address: miyamoto@aki.che.tohoku.ac.jp (A. Miyamoto). www.elsevier.com/locate/micromeso Microporous and Mesoporous Materials 101 (2007) 324–333