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

---

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

Hattori Toshiaki

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.133, no.20, pp.204503, 2010-11

被引用文献数

9

---

A general theoretical framework of two-dimensional time-domain second-order and third-order terahertz spectroscopy has been presented. The theoretical treatment is based on a classical and phenomenological model with weak nonlinearities. Three types of nonlinearity sources, anharmonicity, nonlinear coupling, and nonlinear damping, were considered. The second-order THz spectroscopy has an exact correspondence to fifth-order off-resonance Raman spectroscopy, and it has been shown that the present treatment gives exactly the same results as of the quantum mechanical theory under the weak nonlinearity condition. General expressions for the nonlinear signal have been obtained for a single-mode system, and numerical calculations for delta-function incident terahertz pulses were shown. For the third-order signal, two-level systems were also considered for comparison. Contributions of two types of incident pulse sequences have been studied separately in the third-order signals. Profiles of the two-dimensional signals were found to depend on the origin and order of the nonlinearity and also on the pulse sequence. The results of the present study show that the two-dimensional signal features of second- and third-order nonlinear terahertz spectroscopy can clarify the nature of the system which is not accessible using linear spectroscopy.

著者

Amano Masakazu Yamamura Yasuhisa Sumita Masato Yasuzuka Syuma Kawaji Hitoshi Atake Tooru Saito Kazuya

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.130, no.3, pp.034503, 2009-01

被引用文献数

24 7

---

The heat capacities of single crystals of organic ferroelectric complexes phenazine-chloranilic acid (Phz-H2ca) and phenazine-bromanilic acid (Phz-H2ba) were measured. At temperatures below those of the reported ferroelectric phase transitions,heat capacity anomalies due to successive phase transitions were found in both complexes. Excess entropies involved in the low-temperature successive phase transitions are much larger than those due to the ferroelectric phase transitions. The temperature dependence of the complex dielectric constants showed the existence of multiple dielectric relaxation modes in both complexes and their deuterated analogs (Phz-D2ca and Phz-D2ba). We discuss the possibility of concerted hopping of neighboring protons within a hydrogen-bonded chain while taking into account the one-dimensional nature of the chain.

著者

Yamaoka Yuuki Taniguchi Yuki Yasuzuka Syuma Yamamura Yasuhisa Saito Kazuya

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.135, no.4, pp.044705, 2011-07

被引用文献数

30 12

---

Quasi-binary (QB) picture of thermotropics, which regards a neat thermotropic liquid crystal as a binary system consisting of (semi)rigid core and molten alkyl chain, was assessed experimentally for the most famous (and representative) thermotropic mesogenic series nCB. By adding n-heptane as solvent, the smectic A phase was induced in 7CB–n-heptane system. Small angle x-ray diffraction showed that the QB picture holds not only in the phase behavior but also in the structure. It is suggested that the melting of 8CB and 9CB to isotropic liquid via smectic and nematic liquid crystals can be understood as a thermotropic–lyotropic crossover.

著者

Ikeda Atsushi Miyazaki Kunimasa

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.135, no.2, pp.024901, 2011

被引用文献数

15

---

We numerically study thermodynamic and structural properties of the one-component Gaussian core model at very high densities. The solid-fluid phase boundary is carefully determined. We find that the density dependence of both the freezing and melting temperatures obey the asymptotic relation, log Tf, log Tm∝ − ρ2/3, where ρ is the number density, which is consistent with Stillinger's conjecture. Thermodynamic quantities such as the energy and pressure and the structural functions such as the static structure factor are also investigated in the fluid phase for a wide range of temperature above the phase boundary. We compare the numerical results with the prediction of the liquid theory with the random phase approximation (RPA). At high temperatures, the results are in almost perfect agreement with RPA for a wide range of density, as it has already been shown in the previous studies. In the low temperature regime close to the phase boundary line, although RPA fails to describe the structure factors and the radial distribution functions at the length scales of the interparticle distance, it successfully predicts their behaviors at longer length scales. RPA also predicts thermodynamic quantities such as the energy, pressure, and the temperature at which the thermal expansion coefficient becomes negative, almost perfectly. Striking ability of RPA to predict thermodynamic quantities even at high densities and low temperatures is understood in terms of the decoupling of the length scales which dictate thermodynamic quantities from the interparticle distance which dominates the peak structures of the static structure factor due to the softness of the Gaussian core potential.

著者

Markland Thomas E. Morrone Joseph A. Miyazaki Kunimasa Berne B. J. Reichman David R. Rabani Eran

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.136, no.7, pp.074511, 2012

被引用文献数

34 7

---

A comprehensive microscopic dynamical theory is presented for the description of quantum fluids as they transform into glasses. The theory is based on a quantum extension of mode-coupling theory. Novel effects are predicted, such as reentrant behavior of dynamical relaxation times. These predictions are supported by path integral ring polymer molecular dynamics simulations. The simulations provide detailed insight into the factors that govern slow dynamics in glassy quantum fluids. Connection to other recent work on both quantum glasses as well as quantum optimization problems is presented.

著者

Maczka M. Hanuza J. Baran J. Hushur A. Kojima S.

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.125, no.24, pp.244503, 2006-12

被引用文献数

8

---

The authors report the results of temperature-dependent Brillouin scattering from both transverse and longitudinal acoustic waves, heat capacity studies as well as room temperature Raman scattering studies on M2O–MgO–WO3–P2O5 glasses (M=K,Rb). These results were used to obtain information about structure and various properties of the studied glasses such as fragility, elastic moduli, ratio of photoelastic constants, and elastic anharmonicity. They have found that both glasses have similar properties but replacement of K+ ions by Rb+ ions in the glass network leads to decrease of elastic parameters and P44 photoelastic constant due to increase of fragility. Based on Brillouin spectroscopy they show that a linear correlation between longitudinal and shear elastic moduli holds over a large temperature range. This result supports the literature data that the Cauchy-type relation represents a general rule for amorphous solids. An analysis of the Boson peak revealed that the form of the frequency distribution of the excess density of states is in agreement with the Euclidean random matrix theory. The reason of the observed shift of the maximum frequency of the Boson peak when K+ ions are substituted for Rb+ ions is also briefly discussed.

著者

Kondo Takahiro Kato Hiroyuki S. Bonn Mischa Kawai Maki

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.126, no.18, pp.181103, 2007-05

被引用文献数

28 17

---

The isothermal crystallization process of thin amorphous solid water (ASW) films on Ru(0001) has been investigated in real time by simultaneously employing helium atom scattering, infrared reflection absorption spectroscopy, and isothermal temperature-programmed desorption. The measurements reveal that the crystallization mechanism consists of random nucleation events in the bulk of the ASW films, followed by homogeneous growth. Morphological changes of the solid water film during crystallization expose the water monolayer just above the substrate to the vacuum during the crystallization process.

著者

Shigeta Yasuteru

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.128, no.16, pp.161103, 2008-04

被引用文献数

14 11

---

We have derived a quantum distribution function in terms of cumulants that are expectation values of a (anti)symmetric-ordered product of position and momentum fluctuation operators. A second-order approximation leads a Gaussian distribution function, which is positive definite and has proper marginals so that the Shannon entropy can be evaluated.

著者

Ikeda Atsushi Miyazaki Kunimasa

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.135, no.5, pp.054901, 2011

被引用文献数

27 8

---

We numerically study crystal nucleation and glassy slow dynamics of the one-component Gaussian core model (GCM) at high densities. The nucleation rate at a fixed supercooling is found to decrease as the density increases. At very high densities, the nucleation is not observed at all in the time window accessed by long molecular dynamics (MD) simulation. Concomitantly, the system exhibits typical slow dynamics of the supercooled fluids near the glass transition point. We compare the simulation results of the supercooled GCM with the predictions of mode-coupling theory (MCT) and find that the agreement between them is better than any other model glassformers studied numerically in the past. Furthermore, we find that a violation of the Stokes-Einstein relation is weaker and the non-Gaussian parameter is smaller than canonical glassformers. Analysis of the probability distribution of the particle displacement clearly reveals that the hopping effect is strongly suppressed in the high density GCM. We conclude from these observations that the GCM is more amenable to the mean-field picture of the glass transition than other models. This is attributed to the long-ranged nature of the interaction potential of the GCM in the high density regime. Finally, the intermediate scattering function at small wavevectors is found to decay much faster than its self part, indicating that dynamics of the large-scale density fluctuations decouples with the shorter-ranged caging motion.

著者

Ikeda Atsushi Miyazaki Kunimasa

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.135, no.2, pp.024901, 2011-07

被引用文献数

15 16

---

We numerically study thermodynamic and structural properties of the one-component Gaussian core model at very high densities. The solid-fluid phase boundary is carefully determined. We find that the density dependence of both the freezing and melting temperatures obey the asymptotic relation, log Tf, log Tm∝ − ρ2/3, where ρ is the number density, which is consistent with Stillinger's conjecture. Thermodynamic quantities such as the energy and pressure and the structural functions such as the static structure factor are also investigated in the fluid phase for a wide range of temperature above the phase boundary. We compare the numerical results with the prediction of the liquid theory with the random phase approximation (RPA). At high temperatures, the results are in almost perfect agreement with RPA for a wide range of density, as it has already been shown in the previous studies. In the low temperature regime close to the phase boundary line, although RPA fails to describe the structure factors and the radial distribution functions at the length scales of the interparticle distance, it successfully predicts their behaviors at longer length scales. RPA also predicts thermodynamic quantities such as the energy, pressure, and the temperature at which the thermal expansion coefficient becomes negative, almost perfectly. Striking ability of RPA to predict thermodynamic quantities even at high densities and low temperatures is understood in terms of the decoupling of the length scales which dictate thermodynamic quantities from the interparticle distance which dominates the peak structures of the static structure factor due to the softness of the Gaussian core potential.

著者

Kondo Takahiro Kato Hiroyuki S. Bonn Mischa Kawai Maki

出版者

American Institute of Physics

雑誌

The journal of chemical physics (ISSN:00219606)

巻号頁・発行日

vol.127, no.9, pp.094703, 2007-09

被引用文献数

41 20

---

The deposition and the isothermal crystallization kinetics of thin amorphous solid water (ASW) films on both Ru(0001) and CO-precovered Ru(0001) have been investigated in real time by simultaneously employing helium atom scattering, infrared reflection absorption spectroscopy, and isothermal temperature-programmed desorption. During ASW deposition, the interaction between water and the substrate depends critically on the amount of preadsorbed CO. However, the mechanism and kinetics of the crystallization of ~50 layers thick ASW film were found to be independent of the amount of preadsorbed CO. We demonstrate that crystallization occurs through random nucleation events in the bulk of the material, followed by homogeneous growth, for solid water on both substrates. The morphological change involving the formation of three-dimensional grains of crystalline ice results in the exposure of the water monolayer just above the substrate to the vacuum during the crystallization process on both substrates.

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

---

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.