Gating the conductance of extended metal atom chains: a computational analysis of Ru3(dpa)4(NCS)2 and [Ru3(npa)4(NCS)2].

The effects of a gate potential on the conductance of two members of the EMAC family, Ru3(dpa)4(NCS)2 and its asymmetric analogue, [Ru3(npa)4(NCS)2]+, are explored with a density functional approach combined with non-equilibrium Green's functions. From a computational perspective, the inclusion of an electrochemical gate potential represents a significant challenge because the periodic treatment of the electrode surface resists the formation of charged species. However, it is possible to mimic the effects of the electrochemical gate by including a very electropositive or electronegative atom in the unit cell that will effectively reduce or oxidize the molecule under study. In this contribution we compare this approach to the more conventional application of a solid-state gate potential, and show that both generate broadly comparable results. For two extended metal atom chain (EMAC) compounds, Ru3(dpa)4(NCS)2 and [Ru3(npa)4(NCS)2], we show that the presence of a gate potential shifts the molecular energy levels in a predictable way relative to the Fermi level, with distinct peaks in the conductance trace emerging as these levels enter the bias window.

Quantum chemical models for the absorption of endohedral clusters on Si(111)-(7 × 7): a subtle balance between W-Si and Si-Si bonding.

The link between the intrinsic electronic properties of an endohedral metallo-silicon cluster, W@Si12, its ability to bind to a Si(111)-(7 × 7) surface and the impact on transmission properties is explored using periodic density functional theory. The W 5dz2 orbital, the LUMO of the isolated cluster, plays a critical role in all aspects, forming a covalent bond between the metal and the silicon surface, and then providing an effective transmission channel that allows current to flow from the surface to STM tip. The STM images therefore provide a very direct probe of the W-Si surface bond.

Redox-Dependent Metal-Metal Bonding in Trinuclear Metal Chains: Probing the Transition from Covalent Bonding to Exchange Coupling.

The synthesis and physical properties of two new cationic tri-metallic chains, [(PEt3 )3 RuCl3 M'Cl3 Ru(PEt3 )3 ]1+ , M'=Rh and Ir are reported. These are isostructural with a previously reported 17-electron all-ruthenium analogue, but replacing a d5 RuIII ion in the central position with d6 RhIII /IrIII has a significant impact on the nature of the metal-metal interactions. All three materials have been characterized electrochemically at the 18-, 17- and 16-electron levels. X-ray crystallography and spectroelectrochemistry, complemented by electronic structure analysis at the DFT and CASPT2 levels, indicate that whilst the presence of a RuIII ion in the center of the chain allows multi-center covalent bonding to develop, a closed-shell RhIII /IrIII ion pushes the system towards the exchange-coupled limit, where the outer Ru centers are only weakly interacting. This family of three isostructural compounds reveals how changes in metal composition can have subtle effects on physical properties of systems that lie close to the localized/delocalized borderline.

The role of π-blocking hydride ligands in a pressure-induced insulator-to-metal phase transition in SrVO2H.

Transition-metal oxyhydrides are of considerable current interest due to the unique features of the hydride anion, most notably the absence of valence p orbitals. This feature distinguishes hydrides from all other anions, and gives rise to unprecedented properties in this new class of materials. Here we show via a high-pressure study of anion-ordered strontium vanadium oxyhydride SrVO2H that H- is extraordinarily compressible, and that pressure drives a transition from a Mott insulator to a metal at ~ 50 GPa. Density functional theory suggests that the band gap in the insulating state is reduced by pressure as a result of increased dispersion in the ab-plane due to enhanced Vdπ-Opπ-Vdπ overlap. Remarkably, dispersion along c is limited by the orthogonal Vdπ-H1s-Vdπ arrangement despite the greater c-axis compressibility, suggesting that the hydride anions act as π-blockers. The wider family of oxyhydrides may therefore give access to dimensionally reduced structures with novel electronic properties.

The structural landscape in 14-vertex clusters of silicon, M@Si14: when two bonding paradigms collide.

The structural chemistry of the title clusters has been the source of controversy in the computational literature because the identity of the most stable structure appears to be pathologically dependent on the chosen theoretical model. The candidate structures include a D3h-symmetric 'fullerene-like' isomer with 3-connected vertices (A), an 'arachno' architecture (B) and an octahedral isomer with high vertex connectivities typical of 'closo' electron-deficient clusters (C). The key to understanding these apparently very different structures is the fact that they make use of the limited electron density available from the endohedral metal in very different ways. Early in the transition series the favoured structure is the one that maximises transfer of electron density from the electropositive metal to the cage whereas for later metals it is the one that minimises repulsions with the increasingly core-like d electrons. The varying role of the d electrons across the transition series leads directly to strong functional dependency, and hence to the controversy in the literature.

Biradical character in the ground state of [Mn@Si12](+): a DFT and CASPT2 study.

Both density functional theory and multi-configurational ab initio (CASPT2) calculations are used to explore the potential energy surface of the hexagonal prismatic cluster [Mn@Si12](+). Unlike isoelectronic Cr@Si12, the ground state is a biradical, with triplet and open-shell singlet states lying very close in energy. The results are discussed in the context of recent experimental studies using infra-red multiple photon dissociation spectroscopy and X-ray MCD spectroscopy.

Billion-fold enhancement in sensitivity of nuclear magnetic resonance spectroscopy for magnesium ions in solution.

ß-nuclear magnetic resonance (NMR) spectroscopy is highly sensitive compared to conventional NMR spectroscopy, and may be applied for several elements across the periodic table. ß-NMR has previously been successfully applied in the fields of nuclear and solid-state physics. In this work, ß-NMR is applied, for the first time, to record an NMR spectrum for a species in solution. (31)Mg ß-NMR spectra are measured for as few as 10(7) magnesium ions in ionic liquid (EMIM-Ac) within minutes, as a prototypical test case. Resonances are observed at 3882.9 and 3887.2 kHz in an external field of 0.3 T. The key achievement of the current work is to demonstrate that ß-NMR is applicable for the analysis of species in solution, and thus represents a novel spectroscopic technique for use in general chemistry and potentially in biochemistry.

Computational assignment of redox states to Coulomb blockade diamonds.

With the advent of molecular transistors, electrochemistry can now be studied at the single-molecule level. Experimentally, the redox chemistry of the molecule manifests itself as features in the observed Coulomb blockade diamonds. We present a simple theoretical method for explicit construction of the Coulomb blockade diamonds of a molecule. A combined quantum mechanical/molecular mechanical method is invoked to calculate redox energies and polarizabilities of the molecules, including the screening effect of the metal leads. This direct approach circumvents the need for explicit modelling of the gate electrode. From the calculated parameters the Coulomb blockade diamonds are constructed using simple theory. We offer a theoretical tool for assignment of Coulomb blockade diamonds to specific redox states in particular, and a study of chemical details in the diamonds in general. With the ongoing experimental developments in molecular transistor experiments, our tool could find use in molecular electronics, electrochemistry, and electrocatalysis.

Electric field gradients in Hg compounds: molecular orbital (MO) analysis and comparison of 4-component and 2-component (ZORA) methods.

We examine the performance of Density Functional Theory (DFT) approaches based on the Zeroth-Order Regular Approximation (ZORA) Hamiltonian (with and without inclusion of spin-orbit coupling) for predictions of electric field gradients (EFGs) at the heavy atom Hg nucleus. This is achieved by comparing with benchmark DFT and CCSD-T data (Arcisauskaite et al., Phys. Chem. Chem. Phys., 2012, 14, 2651-2657) obtained from 4-component Dirac-Coulomb Hamiltonian calculations. The investigated set of molecules comprises linear HgL(2) (L = Cl, Br, I, CH(3)) and bent HgCl(2) mercury compounds as well as the trigonal planar [HgCl(3)](-) system. In 4-component calculations we used the dyall.cv3z basis set for Hg, Br, I and the cc-pCVTZ basis set for H, C, Cl, whereas in ZORA calculations we used the QZ4P basis set for all the atoms. ZORA-4 reproduces the fully relativistic 4-component DFT reference values within 6% for all studied Hg compounds and employed functionals (BH&H, BP86, PBE0), whereas scalar relativistic (SR)-ZORA-4 results show deviations of up to 15%. Compared to our 4-component CCSD-T benchmark the BH&H functional performs best at both 4-component and ZORA levels. We furthermore observe that changes in the largest component of the diagonalised EFG tensor, V(zz), of linear HgCl(2) show a slightly stronger dependence than the r(-3) scaling upon bond length r(Hg-Cl) alterations. The 4-component/BH&H V(zz) value of -9.26 a.u. for a bent HgCl(2) (∠Cl-Hg-Cl = 120°) is close to -9.60 a.u. obtained for the linear HgCl(2) structure. Thus a point charge model for EFG calculations completely fails in this case. By means of a projection analysis of molecular orbital (MO) contributions to V(zz) in terms of the atomic constituents, we conclude that this is due to the increased importance of the Hg 5d orbitals upon bending HgCl(2) compared to the linear HgCl(2) structure. Changing ligand leads to only minor changes in V(zz) (from -9.60 a.u. (HgCl(2)) to -8.85 a.u. (HgI(2)) at the 4-component/BH&H level). This appears to be due to cancellation of contributions with opposite signs to V(zz) arising from: (i) increasing electron donation from occupied ligand orbitals to the formally empty Hg 6p orbitals and (ii) an increasing bond length and a decreasing negative charge on the ligand along the series.

Application of 204mPb perturbed angular correlation of γ-rays spectroscopy in coordination chemistry.

(204m)Pb perturbed angular correlation of γ-rays (PAC) spectroscopy has been applied successfully for the first time to detect the nuclear quadrupole interaction in a lead(II) coordination compound in a molecular crystal [tetraphenylarsonium lead(II) isomaleonitriledithiolate ([AsPh(4)](4)[Pb(2)(i-mnt)(4)])]. The recorded parameters from a powder crystalline sample are ν(Q) = 0.178(1) GHz and η = 0.970(7). The electric field gradient (EFG) was determined at the PW91/QZ4P level including relativistic effects using the two-component zeroth-order regular approximation method for both the [Pb(i-mnt)(2)](2-) monomer and the [Pb(2)(i-mnt)(4)](4-) dimer. Only the EFG for the latter compares favorably with the experimental data, indicating that the picture of this complex as a prototypical hemidirected coordination geometry with a stereochemically active lone pair on lead(II) is inadequate. Advantages and limitations of (204m)Pb PAC spectroscopy as a novel technique to elucidate the electronic and molecular structures of lead-containing complexes and biomolecules are presented.

Fully relativistic coupled cluster and DFT study of electric field gradients at Hg in 199Hg compounds.

We investigate the magnitude and interplay of relativistic and electron correlation effects on the electric field gradient (EFG) at the position of Hg in linear and bent HgL(2) (L = CH(3), Cl, Br, I) and trigonal planar [HgCl(3)](-) compounds using four-component relativistic Dirac-Coulomb (DC) and non-relativistic (NR) calculations at the Hartree-Fock (HF), DFT, MP2 and coupled cluster (CC) levels. The relativistic and electron correlation contributions to EFG have opposite signs and are not additive, demonstrating the importance of taking into account relativistic and electron correlation contributions on an equal footing. DC-MP2 overestimates the electron correlation correction by 0.48-0.56 a.u. for Hg-halides and by 0.8 a.u. for Hg(CH(3))(2), respectively, while DC-CCSD underestimates the correlation correction by 0.57-0.66 a.u. compared to the reference DC-CCSD-T data. EFGs obtained at the DC-DFT level vary considerably with the functional; DC-CAMB3LYP and DC-BH&H reproduce DC-CCSD-T results within 0.08-0.24 a.u. (1%-3%) for Hg(CH(3))(2) and Hg-halides, respectively. An updated value of the nuclear quadrupole moment of the I = 5/2 excited state of (199)Hg, Q((199)Hg) = 0.675(12) b is derived from the literature. This value compares well with that derived from our calculated EFG at the DC-CCSD-T level and the experimental data for Hg(CH(3))(2); Q((199)Hg) = 0.650 b.

Nuclear magnetic resonance shielding constants and chemical shifts in linear 199Hg compounds: a comparison of three relativistic computational methods.

We investigate the importance of relativistic effects on NMR shielding constants and chemical shifts of linear HgL(2) (L = Cl, Br, I, CH(3)) compounds using three different relativistic methods: the fully relativistic four-component approach and the two-component approximations, linear response elimination of small component (LR-ESC) and zeroth-order regular approximation (ZORA). LR-ESC reproduces successfully the four-component results for the C shielding constant in Hg(CH(3))(2) within 6 ppm, but fails to reproduce the Hg shielding constants and chemical shifts. The latter is mainly due to an underestimation of the change in spin-orbit contribution. Even though ZORA underestimates the absolute Hg NMR shielding constants by ∼2100 ppm, the differences between Hg chemical shift values obtained using ZORA and the four-component approach without spin-density contribution to the exchange-correlation (XC) kernel are less than 60 ppm for all compounds using three different functionals, BP86, B3LYP, and PBE0. However, larger deviations (up to 366 ppm) occur for Hg chemical shifts in HgBr(2) and HgI(2) when ZORA results are compared with four-component calculations with non-collinear spin-density contribution to the XC kernel. For the ZORA calculations it is necessary to use large basis sets (QZ4P) and the TZ2P basis set may give errors of ∼500 ppm for the Hg chemical shifts, despite deceivingly good agreement with experimental data. A Gaussian nucleus model for the Coulomb potential reduces the Hg shielding constants by ∼100-500 ppm and the Hg chemical shifts by 1-143 ppm compared to the point nucleus model depending on the atomic number Z of the coordinating atom and the level of theory. The effect on the shielding constants of the lighter nuclei (C, Cl, Br, I) is, however, negligible.