Approximate inclusion of four-mode couplings in vibrational coupled-cluster theory

The vibrational coupled cluster (VCC) equations are analyzed in terms of vibrational Mo?ller-Plesset perturbation theory aiming specifically at the importance of four-mode couplings. Based on this analysis, new VCC methods are derived for the calculation of anharmonic vibrational energies and vibrational spectra using vibrational coupled cluster response theory. It is shown how the effect of four-mode coupling and excitations can be efficiently and accurately described using approximations for their inclusion. Two closely related approaches are suggested. The computational scaling of the so-called VCC[3pt4F] method is not higher than the fifth power in the number of vibrational degrees of freedom when up to four-mode coupling terms are present in the Hamiltonian and only fourth order when only up to three-mode couplings are present. With a further approximation, one obtains the VCC[3pt4] model which is shown to scale with at most the fourth power in the number of vibrational degrees of freedom for Hamiltonians with both three- and four-mode coupling levels, while sharing the most important characteristics with VCC[3pt4F]. Sample calculations reported for selected tetra-atomic molecules as well as the larger dioxirane and ethylene oxide molecules support that the new models are accurate and useful.     

Vibrational absorption spectra from vibrational coupled cluster damped linear response functions calculated using an asymmetric Lanczos algorithm

We report the theory and implementation of vibrational coupled cluster (VCC) damped response functions. From the imaginary part of the damped VCC response function the absorption as function of frequency can be obtained, requiring formally the solution of the now complex VCC response equations. The absorption spectrum can in this formulation be seen as a matrix function of the characteristic VCC Jacobian response matrix. The asymmetric matrix version of the Lanczos method is used to generate a tridiagonal representation of the VCC response Jacobian. Solving the complex response equations in the relevant Lanczos space provides a method for calculating the VCC damped response functions and thereby subsequently the absorption spectra. The convergence behaviour of the algorithm is discussed theoretically and tested for different levels of completeness of the VCC expansion. Comparison is made with results from the recently reported [P. Seidler, M. B. Hansen, W. Gyo?rffy, D. Toffoli, and O. Christiansen, J. Chem. Phys. 132, 164105 (2010)] vibrational configuration interaction damped response function calculated using a symmetric Lanczos algorithm. Calculations of IR spectra of oxazole, cyclopropene, and uracil illustrate the usefulness of the new VCC based method.     

Model Identification for Flow Simulations in Geothermal Reservoirs: Towards Optimally Drilling Boreholes

In geothermal reservoir engineering, one is interested in determining the location of boreholes such that measurements taken therein, say temperature, will allow the estimation of unknown parameters such as porosity and permeability. We formulate such a particular borehole location problem and find its solution by techniques from optimal experimental design. More precisely, we minimize the D-optimality criterion to find an optimal location of a single borehole to estimate hydraulic permeability from temperature measurements in two boreholes. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Formation, structure, and reactivity of amino-terminated organic films on silicon substrates

Amino-functionalized organic films were prepared by self-assembling 3-aminopropyltriethoxysilane (APTES) on silicon wafers in either anhydrous toluene or phosphate-buffered saline (PBS) for varied deposition times. Fourier transform infrared spectroscopy (FTIR) and ellipsometry have shown that the structure and thickness of APTES films are governed by the deposition time and reaction solution. Deposition from an anhydrous toluene solution produces APTES films ranging from 10 to 144 A in thickness, depending on the reaction time. FTIR spectra indicate that film growth initially proceeds by adsorption of APTES to the silicon surface followed by siloxane condensation, and after an extended period of time APTES molecules accumulate on the underlying APTES film by either covalent or noncovalent interactions. In contrast, spectroscopically indistinguishable APTES films in thickness ranging from 8 to 13 A were formed when deposition was conducted in aqueous solutions. Measured water contact angles indicate that APTES films deposited in aqueous solutions are more hydrophilic compared to those prepared in toluene solutions. Fluorescence measurements revealed that APTES films prepared in toluene solutions contain more reactive surface amino groups by ca. 3 to 10 times than those prepared in aqueous solutions for the identical reaction time.     

Two-dimensional nucleation of ice from supercooled water

We report the temperature dependent nucleation rates of ice from single water drops supporting aliphatic alcohol Langmuir films. Analysis in the context of a classical theory of heterogeneous nucleation suggests that the critical nucleus is essentially a monolayer, and that the rate-limiting steps in these nucleation processes are therefore not merely influenced by, but instead dictated by, the physics of the water-alcohol interface. Consequently, reduced dimensionality may be much more important in heterogeneous nucleation than has previously been believed.     

Magnetostriction of several high-T c superconductors

We report on magnetostriction measurements of superconducting and nonsuperconducting YBa₂Cu₃O_7– and of two Bi samples with the nominal compositions Bi₂CaSr₂Cu₂O _x and Bi_0.8Pb_0.2Sr_0.8CaCu_1.5O _x . Both types of high temperature superconductors show a nearly identical strongly hysteretic field dependence of the magnetostriction (MS) (l/l+(2–6)*10^–6 at 5 T and 1.5 K). In both cases the MS is a linear function of field in the region 1–5 T, which we explain by striction due to surface currents. Between 1.5 and 35 K the hysteresis of the MS decreases strongly with increasing temperature, which implies a decrease of the pinning force. The MS of quenched nonsuperconducting YBa₂Cu₃O_7– is at least two orders of magnitude smaller than that of the superconductor.