著者

Ishikawa Atsushi Nakashima Hiroyuki Nakatsuji Hiroshi

出版者

American Institute of Physics

雑誌

JOURNAL OF CHEMICAL PHYSICS (ISSN:00219606)

巻号頁・発行日

vol.128, no.12, 2008-03-28

被引用文献数

29

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The nonrelativistic Schrödinger equation and the relativistic four-component Dirac equation of H2+ were solved accurately in an analytical expansion form by the free iterative complement interaction (ICI) method combined with the variational principle. In the nonrelativistic case, we compared the free ICI wave function with the so-called "exact" wave function as two different expansions converging to the unique exact wave function and found that the free ICI method is much more efficient than the exact method. In the relativistic case, we first used the inverse Hamiltonian to guarantee Ritz-type variational principle and obtained accurate result. We also showed that the ordinary variational calculation also gives a nice convergence when the g function is appropriately chosen, since then the free ICI calculation guarantees a correct relationship between the large and small components of each adjacent order, which we call ICI balance. This is the first application of the relativistic free ICI method to molecule. We calculated both ground and excited states in good convergence, and not only the upper bound but also the lower bound of the ground-state energy. The error bound analysis has assured that the present result is highly accurate.

出版者

American Institute of Physics

雑誌

Journal of Chemical Physics (ISSN:00219606)

巻号頁・発行日

vol.125, no.11, 2006-09-21

被引用文献数

14

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The accurate first principles description of the correlations between electrons has been a topic of interest in molecular physics. We have reported in our previous paper [J. Chem. Phys. 123, 144112 (2005)] that the T matrix, which is the ladder diagrams up to the infinite order, can accurately represent the short-range electron correlations while calculating the double ionization energy spectra of atoms and molecules. In this paper, we calculate the two-electron distribution functions of real systems (Ar, CO, CO2, and C2H2) from the eigenvalue equation associated with the Bethe-Salpeter equation for the T matrix by beginning with the local density approximation of the density functional theory and the GW approximation. We found that when the interelectron distance is very small, the Coulomb hole appears between antiparallel spin electrons due to the short-range repulsive Coulomb interaction. The resulting two-electron distribution functions clearly show the Coulomb hole. (c) 2006 American Institute of Physics.

著者

Chen Zhen Nozaki Ryusuke

出版者

American Institute of Physics

雑誌

Journal of Chemical Physics (ISSN:00219606)

巻号頁・発行日

vol.136, no.24, pp.244505, 2012-06-28

被引用文献数

16

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We report here a broadband dielectric spectroscopy study on an ionic liquid microemulsion (ILM) composed of water, Triton X-100 (TX-100), and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6). It is found that the phase behavior of this ILM can be easily identified by its dielectric response. The dielectric behavior of the ILM in the GHz range is consistent with that of TX-100/water mixtures with comparable water-to-TX-100 weight ratio. It consists of the relaxations due to ethylene oxide (EO) unit relaxation, hydration water dynamics, and/or free water dynamics. The water content dependence of the EO unit relaxation suggests that this relaxation involves dynamics of hydration water molecules. In the IL-in-water microemulsion phase, it is found that bmimPF6 molecules are preferentially dissolved in water when their concentration in water is lower than the solubility. An additional dielectric relaxation that is absent in the TX-100/water mixtures is observed in the frequency range of 10^[7]-10^[8] Hz for this ILM. This low-frequency relaxation is found closely related to the bmimPF6 molecule and could be attributed to the hopping of its cations/anions between the anionic/cationic sites.