Theoretical study on aquation reaction of cis-platin complex: RISM-SCF-SEDD, a hybrid approach of accurate quantum chemical method and statistical mechanics

The ligand exchange process of cis-platin in aqueous solution was studied using RISM-SCF-SEDD (reference interaction site model-self-consistent field with spatial electron density distribution) method, a hybrid approach of quantum chemistry and statistical mechanics. The analytical nature of RISM theory enables us to compute accurate reaction free energy in aqueous solution based on CCSD(T), together with the microscopic solvation structure around the complex. We found that the solvation effect is indispensable to promote the dissociation of the chloride anion from the complex.     

Theoretical study of Pt(PR3)(2)(AlCl3) (R = H, Me, Ph, or Cy) including an unsupported bond between transition metal and non-transition metal elements: geometry, bond strength, and prediction

The molecular structure and the binding energy of Pt(PR(3))(2)(AlCl(3)) (R = H, Me, Ph, or Cy) were investigated by DFT, MP2 to MP4(SDTQ), and CCSD(T) methods. The optimized structure of Pt(PCy(3))(2)(AlCl(3)) (Cy = cyclohexyl) by the DFT method with M06-2X and LC-BLYP functionals agrees well with the experimental one. The MP4(SDTQ) and CCSD(T) methods present similar binding energies (BE) of Pt(PH(3))(2)(AlCl(3)), indicating that these methods provide reliable BE value. The DFT(M06-2X)-calculated BE value is close to the MP4(SDTQ) and CCSD(T)-calculated values, while the other functionals present BE values considerably different from the MP4(SDTQ) and CCSD(T)-calculated values. All computational methods employed here indicate that the BE values of Pt(PMe(3))(2)(AlCl(3)) and Pt(PPh(3))(2)(AlCl(3)) are considerably larger than those of the ethylene analogues. The coordinate bond of AlCl(3) with Pt(PR(3))(2) is characterized to be the σ charge transfer (CT) from Pt to AlCl(3). This complex has a T-shaped structure unlike the well-known Y-shaped structure of Pt(PMe(3))(2)(C(2)H(4)), although both are three-coordinate Pt(0) complex. This T-shaped structure results from important participation of the Pt d(σ) orbital in the σ-CT; because the Pt d(σ) orbital energy becomes lower as the P-Pt-P angle decreases, the T-shaped structure is more favorable for the σ-CT than is the Y-shaped structure. [Co(alcn)(2)(AlCl(3))](-) (alcn = acetylacetoneiminate) is theoretically predicted here as a good candidate for the metal complex, which has an unsupported M-Al bond because its binding energy is calculated to be much larger than that of Pt(PCy(3))(2)(AlCl(3)).     

Two-step evaluation of binding energy and potential energy surface of van der Waals complexes

Evaluation of intermolecular distance and binding energy (BE) of van der Waals complex/cluster at ab initio level of theory is computationally demanding when many monomers are involved. Starting from MP2 energy, we reached a two-step evaluation method of BE of van der Waals complex/cluster through reasonable approximations; BE = BE(HF) + sum Mi> Mj{BE (Mi- Mj)(MP2 or MP2.5) - BE(Mi-Mj)(HF)} where HF represents the Hartree-Fock calculation, Mi, Mj, etc. are interacting monomers, and MP2.5 represents the arithmetic mean of MP2 and MP3. The first term is the usual BE of the complex/cluster evaluated at the HF level. The second term is the sum of the difference in two-body BE between the correlated and HF levels of theory. This equation was applied to various van der Waals complexes consisting of up-to-four monomers at MP2 and MP2.5 levels of theory. We found that this method is capable of providing precise estimate of the BE and reproducing well the potential energy surface of van der Waals complexes/clusters; the maximum error of the BE is less than 1 kcal/mol and 1% in most cases except for several limited cases. The origins of error in these cases are discussed in detail.     

A theoretical study of an unusual Y-shaped three-coordinate Pt complex: Pt(0) σ-disilane complex or Pt(II) disilyl complex?

The unusual Y-shaped structure of the recently reported three-coordinate Pt complex Pt[NHC(Dip)(2)](SiMe(2)Ph)(2) (NHC = N-heterocyclic carbene; Dip = 2,6-diisopropylphenyl) was considered a snapshot of the reductive elimination of disilane. A density functional theory study indicates that this structure arises from the strong trans influence of the extremely σ-donating carbene and silyl ligands. Though this complex can be understood to be a Pt(II) disilyl complex bearing a distorted geometry due to the Jahn-Teller effect, its (195)Pt NMR chemical shift is considerably different from those of Pt(II) complexes but close to those of typical Pt(0) complexes. Its Si···Si bonding interaction is ~50% of the usual energy of a Si-Si single bond. The interaction between the Pt center and the (SiMe(2)Ph)(2) moiety can be understood in terms of donation and back-donation interactions of the Si-Si σ-bonding and σ*-antibonding molecular orbitals with the Pt center. Thus, we conclude that this is likely a Pt(0) σ-disilane complex and thus a snapshot after a considerable amount of the charge transfer from disilane to the Pt center has occurred. Phenyl anion (Ph(-)) and [R-Ar](-) [R-Ar = 2,6-(2,6-iPr(2)C(6)H(3))(2)C(6)H(3)] as well as the divalent carbon(0) ligand C(NHC)(2) also provide similar unusual Y-shaped structures. Three-coordinate digermyl, diboryl, and silyl-boryl complexes of Pt and a disilyl complex of Pd are theoretically predicted to have similar unusual Y-shaped structures when a strongly donating ligand coordinates to the metal center. In a trigonal-bipyramidal Ir disilyl complex [Ir{NHC(Dip)(2)}(PH(3))(2)(SiMe(3))(2)](+), the equatorial plane has a similar unusual Y-shaped structure. These results suggest that various snapshots can be shown for the reductive eliminations of the Ge-Ge, B-B, and B-Si σ-bonds.     

Simultaneous measurement of velocity and pressure in a plane jet

A new technique was developed for the simultaneous measurement of velocity and pressure in turbulent flows. To accomplish this objective, a new probe (hereafter called the combined probe) that consists of an X-type hot-wire probe and a newly devised pressure probe was developed. The pressure probe was miniaturized by the MEMS fabrication process and by using a 0.1-in. microphone as a pressure sensor for improving the spatial resolution. This pressure probe was placed between two hot-wire sensors of which the X-type hot-wire probe was composed. The pressure probe was given a hemispherical tip, like that of a pitot tube, because an earlier pressure probe with a conical tip suffered from a reduction in spatial resolution. The spatial arrangement of the pressure probe and the hot-wire probe for the combined probe was carefully determined, because there was a risk that the measurement accuracy of one probe will be influenced by disturbances caused by the other probe when the two probes were placed very close to each other. Therefore, the combined probe was arranged to engender no noticeable interference between the velocity data and the pressure data measured by their respective probes. As one application of this combined probe, simultaneous measurements of pressure and two components of instantaneous velocity were performed in a plane jet. The turbulent energy budget and the cross-correlation coefficient of velocity and pressure in the intermittent region of the plane jet were estimated. The results show that the mean streamwise velocity, velocity fluctuation, and pressure fluctuation profiles were consistent with those measured individually using the X-type hot-wire probe or pressure probe. Moreover, it was shown that the integral value of the diffusion term (which should theoretically be equal to zero) in the turbulent energy transport equation was closer to zero than previous reports (Bradbury in J Fluid Mech 23(Part 1):31–64, 1965). In addition, the time variation of the cross-correlation coefficient in the intermittent region supports the vortex structure model predicted in previous studies (Browne et?al. in J Fluid Mech 149:355–373, 1984; Tanaka et?al. JSME Int J Ser B 49(4):899–905, 2006; Sakai et?al. J Fluid Sci Technol 2(3):611–622, 2007).     

Development of an energy‐domain 57Fe‐Mössbauer spectrometer using synchrotron radiation and its application to ultrahigh‐pressure studies with a diamond anvil cell

An energy‐domain ⁵⁷Fe‐Mössbauer spectrometer using synchrotron radiation (SR) with a diamond anvil cell (DAC) has been developed for ultrahigh‐pressure measurements. The main optical system consists of a single‐line pure nuclear Bragg reflection from an oscillating ⁵⁷FeBO₃ single crystal near the Néel temperature and an X‐ray focusing device. The developed spectrometer can filter the Doppler‐shifted single‐line ⁵⁷Fe‐Mössbauer radiation with a narrow bandwidth of neV order from a broadband SR source. The focused incident X‐rays make it easy to measure a small specimen in the DAC. The present paper introduces the design and performance of the SR ⁵⁷Fe‐Mössbauer spectrometer and its demonstrative applications including the newly discovered result of a pressure‐induced magnetic phase transition of polycrystalline ⁵⁷Fe₃BO₆ and an unknown high‐pressure phase of Gd⁵⁷Fe₂ alloy placed in a DAC under high pressures up to 302 GPa. The achievement of Mössbauer spectroscopy in the multimegabar range is of particular interest to researchers studying the nature of the Earth's core.     

Ionography of nanostructures with the use of a laser plasma of cluster targets

It has been shown that a femtosecond plasma of cluster targets is an almost isotropic source of fast ions and, hence, can be used to obtain ionographic images with a wide field of view. The spatial resolution of the resulting ionographic images is no worse than 600 nm, which corresponds to a uniquely high value of about 105 of the ratio of the field of view to the resolution. The use of 100–300-keV ion fluxes ensures the sensitivity of the method to the sample thickness of no worse than 100 nm even for samples consisting of light chemical elements (C, H). The proposed method can be used to obtain images of low-contrast biological objects, thin films, membranes, and other nanostructured objects.     

Kinetic and theoretical studies of metal ion adsorption in KDP solution

Metal ion adsorption in saturated aqueous potassium dihydrogen phosphate solution was analyzed using kinetic, equilibrium model and computational chemistry approaches. The isotherm constants (K_F and n) in the Freundlich model and the first order Lagergren kinetic model parameter k assist with a general understanding of the fundamental adsorption behavior of trivalent and divalent metal ions. The electrostatic force based on electrostatic potential distribution was found to be an essential feature for metal ion adsorption via a correlation between the ESP values of each metal ion and these experimental parameters.     

Influence of Thomson effect on the resultant local Seebeck coefficient in thermoelectric composite materials

The resultant local Seebeck coefficient α _R (=α _S−α _T) at the interface of a thermoelement has not yet been measured, although it is an important factor governing the thermoelectric efficiency, where α _S is the local Seebeck coefficient and α _T is the one caused by the Thomson effect. It is shown in this paper that α _S, α _T, and α _R of the p- and n-type Cu/Bi–Te/Cu composites are obtained analytically and experimentally on the assumption that the local temperature of the composite on which the temperature difference ΔT is imposed varies linearly with changes in position along the composite. They were indeed estimated as a function of position from the local experimental data of R,ΔI,ΔT, and V generated by applying an additional current of ±I to the composite, where R is the electrical resistance and ΔI is a current generated by the composite. As a result, it was found that the absolute values of α _S at the hot interface of the p- and n-type composites are approximately 1.5 and 1.4 times higher than their lowest values in the middle region of the composite, respectively, while those of α _T are less than 8% of α _S all over the composite and are so small that the relation α _R≈α _S can be held. We thus succeeded in measuring α _R at the interfaces of the composite.