Electronic states of NaLi molecule: Benchmark results with Fock space coupled cluster approach.

Accurate potential energy curves (PECs) are obtained for 20 lowest lying electronic states of the NaLi molecule. The computational scheme used here is based on the multireference coupled cluster theory formulated in the (2,0) sector of the Fock space. The latter sector provides the description of states obtained by attachment of two electrons to the reference system. This makes it possible to adopt the doubly ionized NaLi+2 molecule as a Fermi vacuum. The latter has a very concrete advantage in calculations of the PECs since it dissociates into closed shell fragments (NaLi+2 → Na+ + Li+); hence, the restricted Hartree-Fock method can be used within the whole range of interatomic distances. Computed PECs and spectroscopic constants stay very close to the experimental values (if the latter are available) with the accuracy exceeding the other theoretical approaches including those based on the effective core polarization potentials. Relativistic corrections included at the infinite-order two-component level have a non-negligible effect on the accuracy of computed excitation and dissociation energies with contributions up to 50 cm-1.

Extension of the Fock-space coupled-cluster method with singles and doubles to the three-valence sector.

The single-reference coupled-cluster method has proven very effective in the ab initio description of atomic and molecular systems, but its successful application is limited to states dominated by a single Slater determinant, which is used as the reference. In cases where several determinants are important in the wave function expansion, i.e., we have to deal with nondynamic correlation effects, a multi-reference version of the coupled-cluster method is required. The multi-reference coupled-cluster approaches are based on the effective Hamiltonian formulation providing a two-step procedure, in which dynamic correlation effects can be efficiently evaluated by the wave operator, while nondynamic correlation contributions are given by diagonalization of the effective Hamiltonian in the final step. There are two classical multi-reference coupled-cluster formulations. In this paper, the focus is on the so-called Fock-space coupled-cluster method in its basic version with one- and two-particle operators in the exponent. Computational schemes using this truncation of the cluster operator have been successfully applied in calculations in one- and two-valence sectors of the Fock space. In this paper, we show that the approach can be easily extended and effectively employed in the three-valence sector calculations.

Potential Energy Curves for the Low-Lying Electronic States of K2+ from ab Initio Calculations with All Electrons Correlated.

The electron affinity (EA) calculations based on the equation-of-motion coupled cluster method proved to be an efficient scheme in the treatment of potential energy curves (PECs) for alkali molecular ions, Me2+. The EA approach provides description of states obtained by an attachment of one electron to the reference, which for the Me2+ is a doubly ionized Me2+2 system. The latter has a very concrete advantage in the calculations of the PECs, since it dissociates into the closed-shell fragments (Me2+2 → Me+ + Me+); hence, the restricted Hartree-Fock reference can be used in the whole range of interatomic distances. In this work accurate PECs and spectroscopic constants are obtained for the six lowest-lying electronic states of the K2+ ion. The relativistic effects are included by adding appropriate terms of the Douglas-Kroll Hamiltonian to the one-electron integrals.

Morphometric and mechanical characteristics of Equisetum hyemale stem enhance its vibration.

MAIN CONCLUSION: The order of the internodes, and their geometry and mechanical characteristics influence the capability of the Equisetum stem to vibrate, potentially stimulating spore liberation at the optimum stress setting along the stem. Equisetum hyemale L. plants represent a special example of cellular solid construction with mechanical stability achieved by a high second moment of area and relatively high resistance against local buckling. We proposed the hypothesis that the order of E. hyemale L. stem internodes, their geometry and mechanical characteristics influence the capability of the stem to vibrate, stimulating spore liberation at the minimum stress setting value along the stem. An analysis of apex vibration was done based on videos presenting the behavior of an Equisetum clump filmed in a wind tunnel and also as a result of excitation by bending the stem by 20°. We compared these data with the vibrations of stems of the same size but deprived of the three topmost internodes. Also, we created a finite element model (FEM), upon which we have based the 'natural' stem vibration as a copy of the real object, 'random' with reshuffled internodes and 'uniform', created as one tube with the characters averaged from all internodes. The natural internode arrangement influences the frequency and amplitude of the apex vibration, maintaining an equal stress distribution in the stem, which may influence the capability for efficient spore spreading.

Equation-of-motion coupled cluster method for the description of the high spin excited states.

The equation-of-motion (EOM) coupled cluster (CC) approach in the version applicable for the excitation energy(EE) calculations has been formulated for high spin components. The EE-EOM-CC scheme based on the restricted Hartree-Fock reference and standard amplitude equations as used in the Davidson diagonalization procedure yields the singlet states. The triplet and higher spin components require separate amplitude equations. In the case of quintets, the relevant equations are much simpler and easier to solve. Out of 26 diagrammatic terms contributing to the R1 and R2 singlet equations in the case of quintets, only R2 operator survives with 5 diagrammatic terms present. In addition all terms engaging three body elements of the similarity transformed Hamiltonian disappear. This indicates a substantial simplification of the theory. The implemented method has been applied to the pilot study of the excited states of the C2 molecule and quintet states of C and Si atoms.

Are trichomes involved in the biomechanical systems of Cucurbita leaf petioles?

MAIN CONCLUSION: Trichomes are involved in petiole movement and likely function as a part of the plant biomechanical system serving as an additional reservoir of hydrostatic pressure. The large, non-glandular trichomes on Cucurbita petioles occur across collenchyma strands. Time-lapse imaging was used to study the leaf reorientation of Cucurbita maxima 'Bambino' plants placed in horizontal position. The experiment comprised four variants of the large non-glandular petiole trichomes: (1) intact, (2) mechanically removed, (3) dehydrated, and (4) intact but with longitudinally injured petioles. Isolated strands of collenchyma with intact epidermis or epidermis mechanically removed from the abaxial and adaxial sides of the petiole were subjected to breaking test. The stiffness of the non-isolated tissue with intact epidermis was measured using the micro-indentation method. Petioles without trichomes did not exhibit tropic response, and the dehydration of trichomes slowed and prevented complete leaf reorientation. Isolated strands of collenchyma showed no correlation between strength values and position on the petiole. However, strands of collenchyma with epidermis exhibited a significantly greater strength regardless of their position on the petiole. The indentation test showed that non-isolated collenchyma is stiffer on the abaxial side of the petiole. Trichomes from the abaxial side of the petiole were larger at their base. The application of the 'tensile triangles method' revealed that these trichomes had a biomechanically optimized shape in comparison to the adaxial side. We conclude that trichomes can be involved in plant biomechanical system and serve as an additional reservoir of hydrostatic pressure that is necessary for maintaining petioles in the prestressed state.

Equation-of-motion coupled cluster method for high spin double electron attachment calculations.

The new formulation of the equation-of-motion (EOM) coupled cluster (CC) approach applicable to the calculations of the double electron attachment (DEA) states for the high spin components is proposed. The new EOM equations are derived for the high spin triplet and quintet states. In both cases the new equations are easier to solve but the substantial simplification is observed in the case of quintets. Out of 21 diagrammatic terms contributing to the standard DEA-EOM-CCSDT equations for the R2 and R3 amplitudes only four terms survive contributing to the R3 part. The implemented method has been applied to the calculations of the excited states (singlets, triplets, and quintets) energies of the carbon and silicon atoms and potential energy curves for selected states of the Na2 (triplets) and B2 (quintets) molecules.

First Principle Calculations of the Potential Energy Curves for Electronic States of the Lithium Dimer.

A multireference coupled cluster (CC) approach formulated in the (2,0) sector of the Fock space (FS) is applied to study electronic states of the Li2 molecule. The CC model including single (S) and double (D) excitations from the reference configuration is considered. The FS-CCSD(2,0) method is applicable to the description of the double electron attached states, which implies that in the neutral molecule studies the doubly ionized reference should be adopted. The results of this study include potential energy curves (PECs) and selected spectroscopic constants for 34 electronic states correlating to five lowest dissociation limits of Li2. Both the PECs and the computed spectroscopic constants agree very well with the experimental data wherever the latter are available. This indicates that the rigorous ab initio method can be successfully applied to study the energetics and molecular properties of the alkali metal diatomics.

Adsorption kinetics of ultrathin polymer films in the melt probed by dielectric spectroscopy and second-harmonic generation.

We studied the adsorption kinetics of supported ultrathin films of dye-labeled polystyrene (l-PS) by combining dielectric spectroscopy (DS) and the interface-specific nonlinear optical second harmonic generation (SHG) technique. While DS is sensitive to the fraction of mobile dye moieties (chromophores), the SHG signal probes their anisotropic orientation. Time-resolved measurements were performed above the glass transition temperature on two different sample geometries. In one configuration, the l-PS layer is placed in contact with the aluminum surface, while in the other one, the deposition is done on a strongly adsorbed layer of neat PS. From the time dependence of the dielectric strength and SHG signal of the l-PS layer in contact with the metal, we detected two different kinetics regimes. We interpret these regimes in terms of the interplay between adsorption and orientation of the adsorbing labeling moieties. At early times, dye moieties get adsorbed adopting an orientation parallel to the surface. When adsorption proceeds to completeness, the kinetics slows down and the dye moieties progressively orient normal to the surface. Conversely, when the layer of l-PS layer is deposited on the strongly adsorbed layer of neat PS, both the dielectric strength and the SHG signal do not show any variation with time. This means that no adsorption takes place.

Multireference Double Electron Attached Coupled Cluster Method with Full Inclusion of the Connected Triple Excitations: MR-DA-CCSDT.

The multireference (MR) double electron attached (DA) coupled cluster (CC) method with full inclusion of the connected triple excitations has been applied to study various kinds of MR situations. The MR-DA-CCSDT (S, Singles; D, Doubles; T, Triples) equations have been derived and implemented in an efficient way with n(6) scaling for the target multireference states. They can be used for producing potential energy curves (PECs) for some classes of molecules, e.g., when double molecular cations separate into two closed shell fragments, illustrated with the example of the Na2 molecule. Correct PECs have also been obtained on dissociation of the N-N and C-C bonds in N2H4 and C2H6 molecules, respectively. Another application is the behavior of the molecular energy when we change dihedral angle in the ethylene molecule: with the MR-DA-CC, we see immediate improvement of the results with smooth, cusp free, behavior around the 90° region.

Excited and ionized states of the ozone molecule with full triples coupled cluster methods.

The role of connected triple excitations in coupled cluster (CC) calculations of vertical excitation energies, ionization potentials, and the electron affinity of the ozone molecule is evaluated. The equation of motion (EOM) and Fock space (FS) multireference CC approaches with full triples have been used in the calculations. The effect of the T(3) and R(3) operators significantly improve the EOM CCSD results for all considered quantities. A similar behavior is observed in the case of the FS-CC calculations. The FS-CC calculations with full triples have been obtained only for the intermediate Hamiltonian realization of the FS approach as the standard formulation diverges. The latter results are rigorously linked, and less expensive since smaller matrices are diagonalized.

Cognitive ability experiment with photosensitive organic molecular thin films.

We present an optical experiment which permits us to evaluate the information exchange necessary to self-induce cooperatively a well-organized pattern in a randomly activated molecular assembly. A low-power coherent beam carrying polarization and wavelength information is used to organize a surface relief grating on a photochromic polymer thin film which is photoactivated by a powerful incoherent beam. We demonstrate experimentally that less than 1% of the molecules possessing information cooperatively transmit it to the entire photoactivated polymer film.

Molecular applications of the intermediate Hamiltonian Fock-space coupled-cluster method for calculation of excitation energies.

The intermediate Hamiltonian Fock-space coupled-cluster (FS-CC) method with singles and doubles is applied to calculate vertical excitation energies (EEs) for some molecular systems. The calculations are performed for several small molecules, such as H2O, N2, and CO, and for larger systems, such as C2H4, C4H6, and C6H6. Due to the intermediate Hamiltonian formulation, which provides a robust computational scheme for solving the FS-CC equations, and the efficient factorization strategy, relatively large basis sets and model spaces are employed permitting a comparison of the calculated vertical EEs with the experimental data.

Where does the planar-to-nonplanar turnover occur in small gold clusters?

Several levels of theory, including both Gaussian-based and plane wave density functional theory (DFT), second-order perturbation theory (MP2), and coupled cluster methods (CCSD(T)), are employed to study Au6 and Au8 clusters. All methods predict that the lowest energy isomer of Au6 is planar. For Au8, both DFT methods predict that the two lowest isomers are planar. In contrast, both MP2 and CCSD(T) predict the lowest Au8 isomers to be nonplanar.

Nonlocal communication with photoinduced structures at the surface of a polymer film.

Nonlocal communication between two laser light beams is experimented in a photochromic polymer thin films. Information exchange between the beams is mediated by the self-induction of a surface relief pattern. The exchanged information is related to the pitch and orientation of the grating. Both are determined by the incident beam. The process can be applied to experiment on a new kind of logic gates.