Rhenium-to-benzoylpyridine and rhenium-to-bipyridine MLCT excited states offac-[Re(Cl)(4-benzoylpyridine)2(CO)3] andfac-[Re(4-benzoylpyridine)(CO)3(bpy)]+: a time-resolved spectroscopic and spectroelectrochemical study

The lowest allowed electronic transition of fac-[Re(Cl)(CO)(3)(bopy)(2)] (bopy = 4-benzoylpyridine) has a Re --> bopy MLCT character, as revealed by UV-vis and stationary resonance Raman spectroscopy. Accordingly, the lowest-lying, long-lived, excited state is Re --> bopy (MLCT)-M-3. Electronic depopulation of the Re(CO)(3) unit and population of a bopy pi* orbital upon excitation are evident by the upward shift of v(Cequivalent toO) vibrations and a downward shift of the ketone v(C=O) vibration, respectively, seen in picosecond time-resolved IR spectra. Moreover, reduction of a single bopy ligand in the (MLCT)-M-3 excited state is indicated by time-resolved visible and resonance Raman (TR3) spectra that show features typical of bopy(.-). In contrast, the lowest allowed electronic transition and lowest-lying excited state of a new complex fac-[Re(bopy)(CO)(3)(bpy)](+) (bpy = 2,2'-bipyridine) have been identified as Re --> bpy MLCT with no involvement of the bopy ligand, despite the fact that the first reduction of this complex is bopy-localized, as was proven spectroelectrochemically. This is a rare case in which the localizations of the lowest MLCT excitation and the first reduction are different. (MLCT)-M-3 excited states of both fac-[Re(Cl)(CO)(3)(bopy)(2)] and fac-[Re(bopy)(CO)(3)(bpy)](+) are initially formed vibrationally hot. Their relaxation is manifested by picosecond dynamic shifts of v(Cequivalent toO) IR bands. The X-ray structure of fac-[Re(bopy)(CO)(3)(bpy)](PF6CH3CN)-C-. has been determined.

Energy substitutability in transition agriculture: estimates and implications for Hungary

Subsidised energy prices in pre-transition Hungary had led to excessive energy intensity in the agricultural sector. Transition has resulted in steep input price increases. In this study, Allen and Morishima elasticities of substitution are estimated to study the effects of these price changes on energy use, chemical input use, capital formation and employment. Panel data methods, Generalised Method of Moments (GMM) and instrument exogeneity tests are used to specify and estimate technology and substitution elasticities. Results indicate that indirect price policy may be effective in controlling energy consumption. The sustained increases in energy and chemical input prices have worked together to restrict energy and chemical input use, and the substitutability between energy, capital and labour has prevented the capital shrinkage and agricultural unemployment situations from being worse. The Hungarian push towards lower energy intensity may be best pursued through sustained energy price increases rather than capital subsidies. (C) 2003 Elsevier B.V. All rights reserved.

A variational method for the calculation of spin-rovibronic energy levels of any triatomic molecule in an electronic triplet state

The triatomic spin-rovibronic variational code RVIB3 has been extended to include the effect of two uncoupled electrons, for both (3)Sigma(-) and (3)Pi (Renner-Teller) electronic states. The spin-orbital-rotational kinetic energy is included in the usual way, via terms (J+L+S). The phenomenological terms AL.S and lambda 2/3(3S(z)(2)) are introduced to reproduce the 3 spin-orbit and spin-spin splittings, respectively. Calculations are performed to evaluate the spin-rovibronic energy levels of CCO (X) over tilde (3) Sigma(-) and CCO (A) over tilde (3) Pi for which the Born-Oppenheimer potentials are derived from high-accuracy ab initio calculations.

Vibrational energy levels for the electronic ground state of the diazocarbene (CNN) molecule

The vibrational energy levels of diazocarbene (diazomethylene) in its electronic ground state, (X) over tilde (3) Sigma(-) CNN, have been predicted using the variational method. The potential energy surfaces of (X) over tilde (3) A" CNN were determined by employing ab initio single reference coupled cluster with single and double excitations (CCSD), CCSD with perturbative triple excitations [CCSD(T)], multi-reference complete active space self-consistent-field (CASSCF), and internally contracted multi-reference configuration interaction (ICMRCI) methods. The correlation-consistent polarised valence quadruple zeta (cc-pVQZ) basis set was used. Four sets of vibrational energy levels determined from the four distinct analytical potential functions have been compared with the experimental values from the laser-induced fluorescence measurements of Wurfel et al. obtained in 1992. The CCSD, CCSD(T), and CASSCF potentials have not provided satisfactory agreement with the experimental observations. In this light, the importance of both non-dynamic (static) and dynamic correlation effects in describing the ground state of CNN is emphasised. Our best theoretical fundamental frequencies at the cc-pVQZ ICMRCI level of theory, v(1) = 1230, v(2) = 394, and v(3) = 1420 cm(-1) are in excellent agreement with the experimental values of v(1) = 1235, v(2) = 396, and v(3) = 1419cm(-1) and the mean absolute deviation between the 23 calculated and experimental vibrational energy levels is only 7.4 cm(-1). It is shown that the previously suggested observation of the v(3) frequency at about 2847cm(-1) was in fact the first overtone 2v(3).

Theoretical rovibrational line intensities in the electronic ground state of ozone

First-principles calculations of absolute line intensities and rovibrational energies of ozone (O-16(3)) are reported using potential energy and electric dipole moment functions calculated by the internally contracted MRCI approach. The rovibrational energies and eigenfunctions (up to about 8500 cm(-1) and J = 64) were obtained variationally with an exact Hamiltonian in internal valence coordinates. More than 4.8 x 10(6) electric dipole transition matrix elements were calculated for the absolute rovibrational line intensities. They are compared with the values of the HITRAN database. The purely rotational absolute line intensities in the (000) state and the rovibrational intensities for the (001)-(000) band agree to within about 0.3 to 1% for the (0 10)-(000) band to within about 3 to 4%. Excellent agreement with experiment is also achieved for low-lying overtone and combination bands. Inconsistencies are found for the (100)-(000) band overlapping with the antisymmetric stretching fundamental and also for the (002)-(000) antisymmetric stretching overtone. The generated dipole moment function can be used for predicting the absorption intensities in any of the heavier isotopomers, hot bands or the rates of spontaneous emission.

Ruthenium complexes of C,C '-bis(ethynyl)carboranes: an investigation of electronic interactions mediated by spherical pseudo-aromatic spacers

The complexes [Ru(1-C=C-1,10-C2B8H9)(dppe)Cp*] (3a), [Ru(1-C C-1,12-C2B10H11)(dppe)-Cp*] (3b), [{Ru(dppe)Cp*}(2){mu-1,10-(C C)(2)-1,10-C2B8H8}] (4a) and [{Ru(dppe)Cp*}(2){mu-1,12-(C C)2- 1,12-C2B10-H-10}] (4b), which form a representative series of mono- and bimetallic acetylide complexes featuring 10- and 12-vertex carboranes embedded within the dethynyl bridging ligand, have been prepared and structurally characterized. In addition, these compounds have been examined spectroscopically (UV-is-NIR, IR) in all accessible redox states. The significant separation of the two, one-electron anodic waves observed in the cyclic voltammograms of the bimetallic complexes 4a and 4b is largely independent of the nature of the electrolyte and is attributed to stabilization of the intermediate redox products [4a](+) and [4b](+) through interactions between the metal centers across a distance of ca. 12.5 angstrom. The mono-oxidized bimetallic complexes (4a](+) and [4b](+) exhibit spectroscopic properties consistent with a description of these species in terms of valence-localized (class II) mixed-valence compounds, including a unique low-energy electronic absorption band, attributed to an, IVCT-type transition that tails into the IR region. DFT calculations with model systems [4a-H](+) and [4b-H](+) featuring simplified ligand sets reproduce the observed spectroscopic data and localized electronic structures for the mixed-valence cations [4a](+) and [4b](+).

Rovibrational energy levels for the electronic ground state of A1OH

The vibrational-rotational energy levels of aluminum monohydroxide in its electronic ground state, (A) over tilde (1)A' AlOH, have been predicted using the variational method. The potential energy surface of the (X) over tilde (1)A' ground state of AlOH was determined employing the ab initio coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)] and the correlation-consistent polarized valence quadruple zeta (cc-pVQZ) basis set. Low-lying J= 0 and J= 1 vibrational levels are reported. These are analyzed in terms of the quasilinearity of the molecule. Coriolis effects are shown to be significant. We hope that our predictions will be of value in the future when assigning rovibrational transitions in spectroscopic studies. (c) 2006 Elsevier B.V. All rights reserved.

Consequences of N,C,N '- and C,N,N '-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes

The effects of isoelectronic replacement of a neutral nitrogen donor atom by an anionic carbon atom in terpyridine ruthenium(II) complexes on the electronic and photophysical properties of the resulting N,C,N'- and C,N,N'-cyclometalated aryl ruthenium(II) complexes were investigated. To this end, a series of complexes was prepared either with ligands containing exclusively nitrogen donor atoms, that is, [Ru(R-1-tpy)(R-2-tpy)](2+) (R-1, R-2 = H, CO2Et), or bearing either one N,C,N'- or C,N,N'-cyclometalated ligand and one tpy ligand, that is, [Ru(R-1-(NCN)-C-Lambda-N-Lambda)(R-2-tpy)](+) and [Ru(R-1-(CNN)-N-Lambda-N-Lambda)(R-2-tpy)](+), respectively. Single-crystal X-ray structure determinations showed that cyclometalation does not significantly alter the overall geometry of the complexes but does change the bond lengths around the ruthenium(II) center, especially the nitrogen-to-ruthenium bond length trans to the carbanion. Substitution of either of the ligands with electron-withdrawing ester functionalities fine-tuned the electronic properties and resulted in the presence of an IR probe. Using trends obtained from redox potentials, emission energies, IR spectroelectrochemical responses, and the character of the lowest unoccupied molecular orbitals from DFT studies, it is shown that the first reduction process and luminescence are associated with the ester-substituted C,N,N'-cyclometalated ligand in [Ru(EtO2C-(CNN)-N-Lambda-N-Lambda)(tpy)](+). Cyclometalation in an N,C,N'-bonding motif changed the energetic order of the ruthenium d(zx), d(yz), and d(xy) orbitals. The red-shifted absorption in the N,C,N'-cyclometalated complexes is assigned to MLCT transitions to the tpy ligand. The red shift observed upon introduction of the ester moiety is associated with an increase in intensity of low-energy transitions, rather than a red shift of the main transition. Cyclometalation in the C,N,N'-binding motif also red-shifts the absorption, but the corresponding transition is associated with both ligand types. Luminescence of the cyclometalated complexes is relatively independent of the mode of cyclometalation, obeying the energy gap law within each individual series.

Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]− (L2=chelating redox-active π-donor ligand)

In this article we present for the first time accurate density functional theory (DFT) and time-dependent (TD) DFT data for a series of electronically unsaturated five-coordinate complexes [Mn(CO)(3)(L-2)](-), where L-2 stands for a chelating strong pi-donor ligand represented by catecholate, dithiolate, amidothiolate, reduced alpha-diimine (1,4-dialkyl-1,4-diazabutadiene (R-DAB), 2,2'-bipyridine) and reduced 2,2'-biphosphinine types. The single-crystal X-ray structure of the unusual compound [Na(BPY)][Mn(CO)(3)(BPY)]center dot Et2O and the electronic absorption spectrum of the anion [Mn(CO)(3)(BPY)](-) are new in the literature. The nature of the bidentate ligand determines the bonding in the complexes, which varies between two limiting forms: from completely pi-delocalized diamagnetic {(CO)(3)Mn-L-2}(-) for L-2 = alpha-diimine or biphosphinine, to largely valence-trapped {(CO)(3)Mn-1-L-2(2-)}(-) for L-2(2-) = catecholate, where the formal oxidation states of Mn and L-2 can be assigned. The variable degree of the pi-delocalization in the Mn(L-2) chelate ring is indicated by experimental resonance Raman spectra of [Mn(CO)(3)(L-2)](-) (L-2=3,5-di-tBu-catecholate and iPr-DAB), where accurate assignments of the diagnostically important Raman bands have been aided by vibrational analysis. The L-2 = catecholate type of complexes is known to react with Lewis bases (CO substitution, formation of six-coordinate adducts) while the strongly pi-delocalized complexes are inert. The five-coordinate complexes adopt usually a distorted square pyramidal geometry in the solid state, even though transitions to a trigonal bipyramid are also not rare. The experimental structural data and the corresponding DFT-computed values of bond lengths and angles are in a very good agreement. TD-DFT calculations of electronic absorption spectra of the studied Mn complexes and the strongly pi-delocalized reference compound [Fe(CO)(3)(Me-DAB)] have reproduced qualitatively well the experimental spectra. Analyses of the computed electronic transitions in the visible spectroscopic region show that the lowest-energy absorption band always contains a dominant (in some cases almost exclusive) contribution from a pi(HOMO) -> pi*(LUMO) transition within the MnL2 metallacycle. The character of this optical excitation depends strongly on the composition of the frontier orbitals, varying from a partial L-2 -> Mn charge transfer (LMCT) through a fully delocalized pi(MnL2) -> pi*(MnL2) situation to a mixed (CO)Mn -> L-2 charge transfer (LLCT/MLCT). The latter character is most apparent in the case of the reference complex [Fe(CO)(3)(Me-DAB)]. The higher-lying, usually strongly mixed electronic transitions in the visible absorption region originate in the three lower-lying occupied orbitals, HOMO - 1 to HOMO - 3, with significant metal-d contributions. Assignment of these optical excitations to electronic transitions of a specific type is difficult. A partial LLCT/MLCT character is encountered most frequently. The electronic absorption spectra become more complex when the chelating ligand L-2, such as 2,2'-bipyridine, features two or more closely spaced low-lying empty pi* orbitals.

Electronic energy transfer in a dinuclear Ru/Os complex containing a photoresponsive dithienylethene derivative as bridging ligand

In order to build up a multicomponent system able to perform useful light-induced functions, a dithienylethene-bridged heterodinuclear metal complex (Ru/Os) has been prepared. The compound was characterized and its photophysical properties studied in detail.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Methodology To model the energy and greenhouse gas emissions of electronic software distributions

A new electronic software distribution (ESD) life cycle analysis (LCA)methodology and model structure were constructed to calculate energy consumption and greenhouse gas (GHG) emissions. In order to counteract the use of high level, top-down modeling efforts, and to increase result accuracy, a focus upon device details and data routes was taken. In order to compare ESD to a relevant physical distribution alternative,physical model boundaries and variables were described. The methodology was compiled from the analysis and operational data of a major online store which provides ESD and physical distribution options. The ESD method included the calculation of power consumption of data center server and networking devices. An in-depth method to calculate server efficiency and utilization was also included to account for virtualization and server efficiency features. Internet transfer power consumption was analyzed taking into account the number of data hops and networking devices used. The power consumed by online browsing and downloading was also factored into the model. The embedded CO2e of server and networking devices was proportioned to each ESD process. Three U.K.-based ESD scenarios were analyzed using the model which revealed potential CO2e savings of 83% when ESD was used over physical distribution. Results also highlighted the importance of server efficiency and utilization methods.

Solvent-dependent modulation of metal–metal electronic interactions in a dinuclear cyanoruthenate complex: a detailed electrochemical, spectroscopic and computational study

The dinuclear complex [{Ru(CN)4}2(μ-bppz)]4− shows a strongly solvent-dependent metal–metal electronic interaction which allows the mixed-valence state to be switched from class 2 to class 3 by changing solvent from water to CH2Cl2. In CH2Cl2 the separation between the successive Ru(II)/Ru(III) redox couples is 350 mVand the IVCT band (from the UV/Vis/NIR spectroelectrochemistry) is characteristic of a borderline class II/III or class III mixed valence state. In water, the redox separation is only 110 mVand the much broader IVCT transition is characteristic of a class II mixed-valence state. This is consistent with the observation that raising and lowering the energy of the d(π) orbitals in CH2Cl2 or water, respectively, will decrease or increase the energy gap to the LUMO of the bppz bridging ligand, which provides the delocalisation pathway via electron-transfer. IR spectroelectrochemistry could only be carried out successfully in CH2Cl2 and revealed class III mixed-valence behaviour on the fast IR timescale. In contrast to this, time-resolved IR spectroscopy showed that the MLCTexcited state, which is formulated as RuIII(bppz˙−)RuII and can therefore be considered as a mixed-valence Ru(II)/Ru(III) complex with an intermediate bridging radical anion ligand, is localised on the IR timescale with spectroscopically distinct Ru(II) and Ru(III) termini. This is because the necessary electron-transfer via the bppz ligand is more difficult because of the additional electron on bppz˙− which raises the orbital through which electron exchange occurs in energy. DFT calculations reproduce the electronic spectra of the complex in all three Ru(II)/Ru(II), Ru(II)/Ru(III) and Ru(III)/Ru(III) calculations in both water and CH2Cl2 well as long as an explicit allowance is made for the presence of water molecules hydrogen-bonded to the cyanides in the model used. They also reproduce the excited-state IR spectra of both [Ru(CN)4(μ-bppz)]2– and [{Ru(CN)4}2(μ-bppz)]4− very well in both solvents. The reorganization of the water solvent shell indicates a possible dynamical reason for the longer life time of the triplet state in water compared to CH2Cl2.

The troposphere-to-stratosphere transition in kinetic energy spectra and nonlinear spectral fluxes as seen in ECMWF analyses

Global horizontal wavenumber kinetic energy spectra and spectral fluxes of rotational kinetic energy and enstrophy are computed for a range of vertical levels using a T799 ECMWF operational analysis. Above 250 hPa, the kinetic energy spectra exhibit a distinct break between steep and shallow spectral ranges, reminiscent of dual power-law spectra seen in aircraft data and high-resolution general circulation models. The break separates a large-scale ‘‘balanced’’ regime in which rotational flow strongly dominates divergent flow and a mesoscale ‘‘unbalanced’’ regime where divergent energy is comparable to or larger than rotational energy. Between 230 and 100 hPa, the spectral break shifts to larger scales (from n 5 60 to n 5 20, where n is spherical harmonic index) as the balanced component of the flow preferentially decays. The location of the break remains fairly stable throughout the stratosphere. The spectral break in the analysis occurs at somewhat larger scales than the break seen in aircraft data. Nonlinear spectral fluxes defined for the rotational component of the flow maximize between about 300 and 200 hPa. Large-scale turbulence thus centers on the extratropical tropopause region, within which there are two distinct mechanisms of upscale energy transfer: eddy–eddy interactions sourcing the transient energy peak in synoptic scales, and zonal mean–eddy interactions forcing the zonal flow. A well-defined downscale enstrophy flux is clearly evident at these altitudes. In the stratosphere, the transient energy peak moves to planetary scales and zonal mean–eddy interactions become dominant.

Mode-specificity and transition state-specific energy redistribution in the chemisorption of CH4 on Ni{100}

We have investigated methane (CH4) dissociative chemisorption on the Ni{100} surface by first-principles molecular dynamics (MD) simulations. Our results show that this reaction is mode-specific, with the n1 state being the most strongly coupled to efficient energy flow into the reaction coordinate when the molecule reaches the transition state. By performing MD simulations for two different transition state (TS) structures we provide evidence of TS structure-specific energy redistribution in methane chemisorption. Our results are compared with recently reported state-resolved measurement of methane adsorption probability on nickel surfaces, and we find that a strong correlation exists between the highest vibrational efficacy measured on Ni{100} for the n1 state and the calculated highest fractional vibrational energy content in this mode.