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Title: Unrestricted density functional theory based on the fragment molecular orbital method for the ground and excited state calculations of large systems

Abstract

We extended the fragment molecular orbital (FMO) method interfaced with density functional theory (DFT) into spin unrestricted formalism (UDFT) and developed energy gradients for the ground state and single point excited state energies based on time-dependent DFT. The accuracy of FMO is evaluated in comparison to the full calculations without fragmentation. Electronic excitations in solvated organic radicals and in the blue copper protein, plastocyanin (PDB code: 1BXV), are reported. The contributions of solvent molecules to the electronic excitations are analyzed in terms of the fragment polarization and quantum effects such as interfragment charge transfer.

Authors:
 [1];  [2];  [3];  [4];  [1];  [3]
  1. Center for Biological Resources and Informatics, Tokyo Institute of Technology, B-62 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501 (Japan)
  2. NRI, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568 (Japan)
  3. RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)
  4. Graduate School of System Informatics, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501 (Japan)
Publication Date:
OSTI Identifier:
22253292
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 14; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; COPPER; DENSITY FUNCTIONAL METHOD; EXCITATION; EXCITED STATES; GROUND STATES; MOLECULAR ORBITAL METHOD; POLARIZATION; SOLVENTS; TIME DEPENDENCE

Citation Formats

Nakata, Hiroya, RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198, Fedorov, Dmitri G., Yokojima, Satoshi, Tokyo University of Pharmacy and Life Sciences, 1423-1 Horinouchi, Hachioji-shi, Tokyo 192-0392, Kitaura, Kazuo, Sakurai, Minoru, and Nakamura, Shinichiro. Unrestricted density functional theory based on the fragment molecular orbital method for the ground and excited state calculations of large systems. United States: N. p., 2014. Web. doi:10.1063/1.4870261.
Nakata, Hiroya, RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198, Fedorov, Dmitri G., Yokojima, Satoshi, Tokyo University of Pharmacy and Life Sciences, 1423-1 Horinouchi, Hachioji-shi, Tokyo 192-0392, Kitaura, Kazuo, Sakurai, Minoru, & Nakamura, Shinichiro. Unrestricted density functional theory based on the fragment molecular orbital method for the ground and excited state calculations of large systems. United States. https://doi.org/10.1063/1.4870261
Nakata, Hiroya, RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198, Fedorov, Dmitri G., Yokojima, Satoshi, Tokyo University of Pharmacy and Life Sciences, 1423-1 Horinouchi, Hachioji-shi, Tokyo 192-0392, Kitaura, Kazuo, Sakurai, Minoru, and Nakamura, Shinichiro. 2014. "Unrestricted density functional theory based on the fragment molecular orbital method for the ground and excited state calculations of large systems". United States. https://doi.org/10.1063/1.4870261.
@article{osti_22253292,
title = {Unrestricted density functional theory based on the fragment molecular orbital method for the ground and excited state calculations of large systems},
author = {Nakata, Hiroya and RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 and Fedorov, Dmitri G. and Yokojima, Satoshi and Tokyo University of Pharmacy and Life Sciences, 1423-1 Horinouchi, Hachioji-shi, Tokyo 192-0392 and Kitaura, Kazuo and Sakurai, Minoru and Nakamura, Shinichiro},
abstractNote = {We extended the fragment molecular orbital (FMO) method interfaced with density functional theory (DFT) into spin unrestricted formalism (UDFT) and developed energy gradients for the ground state and single point excited state energies based on time-dependent DFT. The accuracy of FMO is evaluated in comparison to the full calculations without fragmentation. Electronic excitations in solvated organic radicals and in the blue copper protein, plastocyanin (PDB code: 1BXV), are reported. The contributions of solvent molecules to the electronic excitations are analyzed in terms of the fragment polarization and quantum effects such as interfragment charge transfer.},
doi = {10.1063/1.4870261},
url = {https://www.osti.gov/biblio/22253292}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 14,
volume = 140,
place = {United States},
year = {Mon Apr 14 00:00:00 EDT 2014},
month = {Mon Apr 14 00:00:00 EDT 2014}
}