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Wojciech Grochala

Publications and source records attributed to Wojciech Grochala.

10 recordsLinked to original sources
PubMed2006

Remarks on catalytic reduction of CO2, H+ and H2 by monovalent Ni.

Prompted by catalysis of CO2 electroreduction by a tetraazamacrocyclic Ni(i)(cyclam) complex (cyclam = 1,4,8,11-tetraazacyclotetradecane), we examine theoretically the possibility of H2 reduction by this molecule. We show that the process 2 Ni(i) + H2 --> 2 [Ni(ii)(H-)] is thermodynamically facile, and that H2 could be reduced by a binuclear Ni(i) complex in two concerted 1e- processes. Our calculations also indicate that hydride complexes of Ni(iii)(cyclam) are significantly unstable thermodynamically and therefore they are unlikely to serve as intermediates in process of H2 evolution from water.

Journal Article↗
PubMed2006

Structures and potential superconductivity in at high pressure: en route to "metallic hydrogen".

A way to circumvent the high pressures needed to metallize hydrogen is to "precompress" it in hydrogen-rich molecules, a strategy probed theoretically for silane. We show that phases with tetrahedral SiH4 molecules should undergo phase transitions with sixfold- and eightfold-coordinate Si appearing above 25 GPa. The most stable structure found can be metallized at under a megabar and at a compression close to the prediction of Goldhammer-Herzfeld criterion. According to a BCS-like estimate, metallic silane should be a high-temperature superconductor.

Journal Article↗
PubMed2005

Towards a tunable molecular memory that fits into a (10 A)3 cube.

Using DFT calculations we predict a novel family of small amino acid-based memory-exhibiting molecules, namely complexes of triply deprotonated cysteine (or its derivatives) with selected hexavalent transition metals. We show that the energy difference of the 0 and 1 electromers--corresponding to two chemically distinct oxidation states of a metal, M(VI) and M(IV)--can be tuned towards the thermodynamic equilibrium via deliberate chemical substitutions in the cysteine ligand. Although the thermal stability of both electromers is computed to be rather small at ambient temperatures (due to facile interchange of states 0 and 1 via a low-lying M(V) configuration), we hope to improve stability in related systems. [Figure: see text]. We propose novel kind of tunable molecular memory, based on intramolecular 2e- redox reaction.

Models, Molecular↗
PubMed2005

Superconductivity: small steps towards the "grand unification".

The existence of various families of super conducting materials and their T(C) values are qualitatively rationalized within a simple model. Novel families of superconducting materials, particularly those based on fluoride and hydride anions, are predicted. [Figure: see text]. We predict that existing families of moderate- and high-T(C) superconductors should hopefully be enriched by novel compounds containing hardly polarizable anions (such as F(-)). Covalent chlorides and hydrides also merit careful exploration.

Electric Conductivity↗
PubMed2003

Vibronic coupling in molecules and in solids.

We utilize the experience gained in our previous studies on the "chemistry of vibronic coupling" in simple homonuclear and heteronuclear molecules to begin assembling theoretical guidelines for the construction of potentially superconducting solids exhibiting large electron-phonon coupling. For this purpose we analyze similarities between vibronic coupling in isolated molecules and in extended solids. In particular, we study vibronic coupling along the antisymmetric stretch coordinate (Q(as)) in linear symmetric AAA molecules, and along the optical phonon "pairing" mode coordinate (Q(opt)) in corresponding one-dimensional [A]( infinity ) chains built of equidistant A atoms. This is done for a broad range of chemical elements (A). The following similarities between vibronic coupling in molecules and phonon coupling in solids emerge from our calculations: 1) The HOMO/LUMO electronic energy gap in an AAA molecule increases along Q(as), and the highest occupied crystal orbital/lowest unoccupied crystal orbital gap in [A]( infinity ) chain increases along Q(opt). 2) The maximum vibronic instability is invariably obtained for a half-filled, singly occupied molecular orbital in AAA molecules, and for a corresponding half-filled band in [A]( infinity ) chains. 3) The vibronic stability of an AAA molecule increases with a decrease of the AA bond length, as does the vibronic stability of [A]( infinity ) chains (external pressure may lead to a reversal of a Peierls distortion). 4) The high degree of s-p mixing and ionic/covalent forbidden curve crossing dramatically enhance the vibronic instability of both AAA molecules and [A]( infinity ) chains. We also introduce one quantitative relationship: The parameter log(R) (where R is molar refractivity, a parameter used by Herzfeld to prescribe the conditions for the metallization of the elements) correlates with a parameter f(AA) (defined as twice the electronegativity of A, divided by the equilibrium AA bond length), used by two of us previously to describe vibronic coupling in AAA molecules for a broad range of elements (A=halogen, H, or an alkali metal). We hope to illustrate that key chemical aspects of vibronic coupling in simple molecules may thus be profitably transferred to corresponding materials in the solid state.

Journal Article↗
PubMed2001

Real and Hypothetical Intermediate-Valence Ag(II)/Ag(III) and Ag(II)/Ag(I) Fluoride Systems as Potential Superconductors.

With the aim of gauging their potential as conducting or superconducting materials, we examine the crystal structures and magnetic properties of the roughly one hundred binary, ternary, and quaternary Ag(II) and Ag(III) fluorides in the solid state reported up to date. The Ag(II) cation appears in these species usually in a distorted octahedral environment, either in an [AgF](+) infinite chain or as [AgF(2)] sheets. Sometimes one finds discrete square-planar [AgF(4)](2-) ions. The Ag(III) cation occurs usually in the form of isolated square-planar [AgF(4)](-) ions. Systems containing Ag(III) (d(8)) centers are typically diamagnetic. On the other hand, the rich spectrum of Ag(II) (d(9)) environments in binary and ternary fluorides leads to most diverse magnetic properties, ranging from paramagnetism, through temperature-independent paramagnetism (characteristic for half-filled band and metallic behavior) and antiferromagnetism, to weak ferromagnetism. Ag(II) and Ag(III) have the same d-electron count as Cu(II) (d(9)) and Cu(III) (d(8)), respectively. F(-) and O(2-) ions are isoelectronic, closed-shell (s(2)p(6)) species; both are weak-field ligands. Led by these similarities, and by some experimental evidence, we examine analogies between the superconducting cuprates (Cu(II)/Cu(III)-O(2-) and Cu(II)/Cu(I)-O(2-) systems) and the formally mixed-valence Ag(II)/Ag(III)-F(-) and Ag(II)/Ag(I)-F(-) phases. For this purpose we perform electronic-structure computations for a number of structurally characterized binary and ternary Ag(I), Ag(II), and Ag(III) fluorides and compare the results with similar calculations for oxocuprate superconductors. Electronic levels in the vicinity of the Fermi level (x(2)-y(2) or z(2)) have usually strongly mixed Ag(d)/F(p) character and are Ag-F antibonding, thus providing the potential of efficient vibronic coupling (typical for d(9) systems with substantially covalent bonds). According to our computations this is the result not only of a coincidence in orbital energies; surprisingly the Ag-F bonding is substantially covalent in Ag(II) and Ag(III) fluorides. The electron density of state at the Fermi level (DOS(F)) for silver fluoride materials and frequencies of the metal-ligand stretching modes have values close to those for copper oxides. The above features suggest that properly hole- or electron-doped Ag(II) fluorides might be good BCS-type superconductors. We analyze a comproportionation/disproportionation equilibrium in the hole-doped Ag(II) fluorides, and the possible appearance of holes in the F(p) band. It seems that there is a chance of generating an Ag(III)-F(-)/Ag(II)-F(0) "ionic/covalent" curve crossing in the hole-doped Ag(II)-F(-) fluorides, significantly increasing vibronic coupling.

Journal Article↗