Luminescence and Energy Transfer of [Ru(bpy) 3 ] 2+ , [Cr(ox) 3 ] 3- , and [Os(bpy) 3 ] 2+ in Three-Dimensional Oxalato-Networks

Luminescence and energy transfer in [Zn1-xRux(bpy)3][NaAl1-yCry(ox)3] (x ≈ 0.01, y = 0.006 − 0.22; bpy = 2,2‘-bipyridine, ox = C2O42-) and [Zn1-x-yRuxOsy(bpy)3][NaAl(ox)3] (x ≈ 0.01, y = 0.012) are presented and discussed. Surprisingly, the luminescence of the isolated luminophores [Ru(bpy)3]2+ and [Os(bpy)3]2+ in [Zn(bpy)3][NaAl(ox)3] is hardly quenched at room temperature. Steady-state luminescence spectra and decay curves show that energy transfer occurs between [Ru(bpy)3]2+ and [Cr(ox)3]3- and between [Ru(bpy)3]2+ and [Os(bpy)3]2+ in [Zn1-xRux(bpy)3][NaAl1-yCry(ox)3] and [Zn1-x-yRuxOsy(bpy)3] [NaAl(ox)3], respectively. For a quantitative investigation of the energy transfer, a shell type model is developed, using a Monte Carlo procedure and the structural parameters of the systems. A good description of the experimental data is obtained assuming electric dipole−electric dipole interaction between donors and acceptors, with a critical distance Rc for [Ru(bpy)3]2+ to [Cr(ox)3]3- energy transfer of 15 Å and for [Ru(bpy)3]2+ to [Os(bpy)3]2+ energy transfer of 33 Å. These values are in good agreement with those derived using the Förster−Dexter theory.

Zeeman effect in atmospheric O₂ measured by ground-based microwave radiometry

In this work we study the Zeeman effect on stratospheric O₂ using ground-based microwave radiometer measurements. The interaction of the Earth magnetic field with the oxygen dipole leads to a splitting of O₂ energy states, which polarizes the emission spectra. A special campaign was carried out in order to measure this effect in the oxygen emission line centered at 53.07 GHz. Both a fixed and a rotating mirror were incorporated into the TEMPERA (TEMPERature RAdiometer) in order to be able to measure under different observational angles. This new configuration allowed us to change the angle between the observational path and the Earth magnetic field direction. Moreover, a high-resolution spectrometer (1 kHz) was used in order to measure for the first time the polarization state of the radiation due to the Zeeman effect in the main isotopologue of oxygen from ground-based microwave measurements. The measured spectra showed a clear polarized signature when the observational angles were changed, evidencing the Zeeman effect in the oxygen molecule. In addition, simulations carried out with the Atmospheric Radiative Transfer Simulator (ARTS) allowed us to verify the microwave measurements showing a very good agreement between model and measurements. The results suggest some interesting new aspects for research of the upper atmosphere.

Solvation-Driven Charge Transfer and Localization in Metal Complexes

In any physicochemical process in liquids, the dynamical response of the solvent to the solutes out of equilibrium plays a crucial role in the rates and products: the solvent molecules react to the changes in volume and electron density of the solutes to minimize the free energy of the solution, thus modulating the activation barriers and stabilizing (or destabilizing) intermediate states. In charge transfer (CT) processes in polar solvents, the response of the solvent always assists the formation of charge separation states by stabilizing the energy of the localized charges. A deep understanding of the solvation mechanisms and time scales is therefore essential for a correct description of any photochemical process in dense phase and for designing molecular devices based on photosensitizers with CT excited states. In the last two decades, with the advent of ultrafast time-resolved spectroscopies, microscopic models describing the relevant case of polar solvation (where both the solvent and the solute molecules have a permanent electric dipole and the mutual interaction is mainly dipole−dipole) have dramatically progressed. Regardless of the details of each model, they all assume that the effect of the electrostatic fields of the solvent molecules on the internal electronic dynamics of the solute are perturbative and that the solvent−solute coupling is mainly an electrostatic interaction between the constant permanent dipoles of the solute and the solvent molecules. This well-established picture has proven to quantitatively rationalize spectroscopic effects of environmental and electric dynamics (time-resolved Stokes shifts, inhomogeneous broadening, etc.). However, recent computational and experimental studies, including ours, have shown that further improvement is required. Indeed, in the last years we investigated several molecular complexes exhibiting photoexcited CT states, and we found that the current description of the formation and stabilization of CT states in an important group of molecules such as transition metal complexes is inaccurate. In particular, we proved that the solvent molecules are not just spectators of intramolecular electron density redistribution but significantly modulate it. Our results solicit further development of quantum mechanics computational methods to treat the solute and (at least) the closest solvent molecules including the nonperturbative treatment of the effects of local electrostatics and direct solvent−solute interactions to describe the dynamical changes of the solute excited states during the solvent response.

The elusive S2 state, the S1/S2 splitting, and the excimer states of the benzene dimer

We observe the weak S 0 → S 2 transitions of the T-shaped benzene dimers (Bz)2 and (Bz-d 6)2 about 250 cm−1 and 220 cm−1 above their respective S 0 → S 1 electronic origins using two-color resonant two-photon ionization spectroscopy. Spin-component scaled (SCS) second-order approximate coupled-cluster (CC2) calculations predict that for the tipped T-shaped geometry, the S 0 → S 2 electronic oscillator strength f el (S 2) is ∼10 times smaller than f el (S 1) and the S 2 state lies ∼240 cm−1 above S 1, in excellent agreement with experiment. The S 0 → S 1 (ππ ∗) transition is mainly localized on the “stem” benzene, with a minor stem → cap charge-transfer contribution; the S 0 → S 2 transition is mainly localized on the “cap” benzene. The orbitals, electronic oscillator strengths f el (S 1) and f el (S 2), and transition frequencies depend strongly on the tipping angle ω between the two Bz moieties. The SCS-CC2 calculated S 1 and S 2 excitation energies at different T-shaped, stacked-parallel and parallel-displaced stationary points of the (Bz)2 ground-state surface allow to construct approximate S 1 and S 2 potential energy surfaces and reveal their relation to the “excimer” states at the stacked-parallel geometry. The f el (S 1) and f el (S 2) transition dipole moments at the C 2v -symmetric T-shape, parallel-displaced and stacked-parallel geometries are either zero or ∼10 times smaller than at the tipped T-shaped geometry. This unusual property of the S 0 → S 1 and S 0 → S 2 transition-dipole moment surfaces of (Bz)2 restricts its observation by electronic spectroscopy to the tipped and tilted T-shaped geometries; the other ground-state geometries are impossible or extremely difficult to observe. The S 0 → S 1/S 2 spectra of (Bz)2 are compared to those of imidazole ⋅ (Bz)2, which has a rigid triangular structure with a tilted (Bz)2 subunit. The S 0 → S 1/ S 2 transitions of imidazole-(benzene)2 lie at similar energies as those of (Bz)2, confirming our assignment of the (Bz)2 S 0 → S 2 transition.

Excitonic splittings in molecular dimers: why static ab initio calculations cannot match them

After decades of research on molecular excitons, only few molecular dimers are available on which exciton and vibronic coupling theories can be rigorously tested. In centrosymmetric H-bonded dimers consisting of identical (hetero)aromatic chromophores, the monomer electronic transition dipole moment vectors subtract or add, yielding S0 → S1 and S0 → S2 transitions that are symmetry-forbidden or -allowed, respectively. Symmetry breaking by 12C/13C or H/D isotopic substitution renders the forbidden transition weakly allowed. The excitonic coupling (Davydov splitting) can then be measured between the S0 → S1 and S0 → S2 vibrationless bands. We discuss the mass-specific excitonic spectra of five H-bonded dimers that are supersonically cooled to a few K and investigated using two-color resonant two-photon ionization spectroscopy. The excitonic splittings Δcalc predicted by ab initio methods are 5–25 times larger than the experimental excitonic splittings Δexp. The purely electronic ab initio splittings need to be reduced (“quenched”), reflecting the coupling of the electronic transition to the optically active vibrations of the monomers. The so-called quenching factors Γ < 1 can be determined from experiment (Γexp) and/or calculation (Γcalc). The vibronically quenched splittings Γ·Δcalc are found to nicely reproduce the experimental exciton splittings.

(O8, O8) contribution to B¯ → Xsγγ at O(αs)

In this analysis, we present the contribution associated with the chromomagnetic dipole operator O8 to the double differential decay width dΓ/(ds1ds2) for the inclusive process B¯→Xsγγ. The kinematical variables s1 and s2 are defined as si=(pb−qi)2/m2b, where pb, q1, q2 are the momenta of b quark and two photons. This contribution (taken at tree level) is of order αs, like the recently calculated QCD corrections to the contribution of the operator O7. In order to regulate possible collinear singularities of one of the photons with the strange quark, we introduce a nonzero mass ms for the strange quark. Our results are obtained for exact ms, which we interpret as a constituent mass being varied between 400 and 600 MeV. Numerically it turns out that the effect of the (O8, O8) contribution to the branching ratio of B¯→Xsγγ does not exceed +0.1% for any kinematically allowed value of our physical cutoff parameter c, confirming the expected suppression of this contribution relative to the QCD corrections to dΓ77/(ds1ds2).

Microwave Spectroscopy and Structures of Several Substituted Acetylenes and Fluorocarbons

The structures of two substituted acetylene compounds have been characterized from their microwave rotational spectra. In the first study, two structures of 6-methyl-3-heptyne have been determined. This compound can be thought of as an ethyl group separated from an isobutyl group by a C≡C spacer. Both structures have the ethyl and isobutyl groups eclipsed, consistent with the dominant interaction determining the orientation about the acetylene axis being the weak dispersion attraction between the end groups. One structure is with the isobutyl group in a symmetric conformation and the other with the isobutyl group asymmetric. In addition, the microwave spectrum of the butane analogue 3,5-octadiyne has been observed. This compound consists of two ethyl groups separated by two C≡C spacers. The study is still in progress, but it appears that the ethyl end groups are freely rotating. Therefore, it seems that the dispersion attractions between the end groups are too weak at this longer distance of about 7 Å. The structures of several fluorocarbons have also been studied by microwave spectroscopy. The structures of perfluoropentane and perfluorohexane have been shown to be helical, like the polymer polytetrafluoroethylene (Teflon©). The structure of perfluoropropane and two conformers of 1H-heptafluoropropane have been determined to be non-helical. It is apparent that the steric and dipole repulsions between fluorine atoms that have been attributed to the helical structure of longer fluorocarbon chains are not sufficient in a three carbon chain to cause a twist in the structures.

Electrostatics for Chemists

This is an introduction to electrostatics written for those interested in dipole moments, induced dipole moments, etc..

(Table 1) Remanence properties of samples from ODP Core 126-792A-7H

A combination of high sedimentation rates and high concentrations of magnetic grains in cores from Ocean Drilling Program Leg 126 resulted in the recovery of detailed direction and intensity records of the Brunhes/Matuyama geomagnetic polarity reversal. Virtual geomagnetic poles (VGPs) computed from azimuthally oriented samples taken from the cores of Hole 792A in the western Izu-Bonin forearc basin reveal that the geomagnetic pole persisted at moderate to high southern latitudes for several thousand years before a rapid migration to northern latitudes. Alternating-field demagnetization behavior, as well as NRM, NRM/ARM, and NRM/IRM intensities for samples from this same interval, and the NRM/IRM intensities derived from unoriented core samples from Holes 790C and 791B, drilled in the ~100-km distant Sumisu Rift, all suggest that the dipole field oscillated widely in intensity before the reversal. The fast polarity change occurred at the low point of an ~1100-yr field intensity cycle. This "reversal cycle" immediately followed earlier intensity cycles whose peaks rivaled or surpassed the normalized intensities of discrete samples from well above and below the reversal interval; furthermore, the troughs indicate a much diminished dipole field at their nadir.

Stable carbon and hydrogen isotope record of n-Alkanoic acids of sediment core SO189/2_144KL

The Indo-Pacific Warm Pool (IPWP) is a key site for the global hydrologic cycle, and modern observations indicate that both the Indian Ocean Zonal Mode (IOZM) and the El Niño Southern Oscillation exert strong influence on its regional hydrologic characteristics. Detailed insight into the natural range of IPWP dynamics and underlying climate mechanisms is, however, limited by the spatial and temporal coverage of climate data. In particular, long-term (multimillennial) precipitation patterns of the western IPWP, a key location for IOZM dynamics, are poorly understood. To help rectify this, we have reconstructed rainfall changes over Northwest Sumatra (western IPWP, Indian Ocean) throughout the past 24,000 y based on the stable hydrogen and carbon isotopic compositions (dD and d13C, respectively) of terrestrial plant waxes. As a general feature of western IPWP hydrology, our data suggest similar rainfall amounts during the Last Glacial Maximum and the Holocene, contradicting previous claims that precipitation increased across the IPWP in response to deglacial changes in sea level and/or the position of the Intertropical Convergence Zone. We attribute this discrepancy to regional differences in topography and different responses to glacioeustatically forced changes in coastline position within the continental IPWP. During the Holocene, our data indicate considerable variations in rainfall amount. Comparison of our isotope time series to paleoclimate records from the Indian Ocean realm reveals previously unrecognized fluctuations of the Indian Ocean precipitation dipole during the Holocene, indicating that oscillations of the IOZM mean state have been a constituent of western IPWP rainfall over the past ten thousand years.

Paleomagnetic of DSDP Leg 91 basalts and sediments

Paleomagnetic studies were carried out on 23 basalt and 74 sediment samples from Leg 91 of the Deep Sea Drilling Project, recovered from a portion of the southwestern Pacific plate (24°S, 166°W) dating back to the Early Cretaceous to perhaps Late Jurassic. The expected geocentric axial dipole inclination at this latitude is -41°. The corrected mean stable inclination of -75° for the basalts indicates a paleolatitude of 63°S for their formation and thus 39° of northward motion during the last 100 m.y. Sediment inclinations steepen rapidly below 13-m depth in the core, suggesting little northward motion of this part of the Pacific plate until about 25 m.y. ago. Examination of the opaque minerals in polished section, as well as the Curie temperatures determined for six basalt samples, reveals no evidence of high- or intermediate-temperature oxidation and thus no reheating of the basement rock since its formation.

PSV records from Tangra Yumco and Taro Co (Tibetan Plateau)

Magnetostratigraphy has been serving as a valuable tool for dating and confirming chronologies of lacustrine sediments in many parts of the world. Suitable paleomagnetic records on the Tibetan Plateau (TP) and adjacent areas are, however, extremely scarce. Here, we derive paleomagnetic records from independently radiocarbon-dated sediments from two lakes separated by 250 km on the southern central TP, Tangra Yumco and Taro Co. Studied through alternating field demagnetization of u-channel samples, characteristic remanent magnetization (ChRM) directions document similar inclination patterns in multiple sediment cores for the past 4000 years. Comparisons to an existing record from Nam Co, a lake 350 km east of Tangra Yumco, a varve-dated record from the Makran Accretionary Wedge, records from Lakes Issyk-Kul and Baikal, and a stack record from East Asia reveal many similarities in inclination. This regional similarity demonstrates the high potential of inclination to compare records over the Tibetan Plateau and eventually date other Tibetan records stratigraphically. PSV similarities over such a large area (>3000 km) suggest a large-scale core dynamic origin rather than small scale processes like drift of the non-dipole field often associated with PSV records.

Paleomagnetic, stable oxygen isotope ratios, and U/Th activities of ODP Site 172-1062

Geomagnetic excursions are recognized as intrinsic features of the Earth's magnetic field. High-resolution records of field behaviour, captured in marine sedimentary cores, present an opportunity to determine the temporal and geometric character of the field during geomagnetic excursions and provide constraints on the mechanisms producing field variability. We present here the highest resolution record yet published of the Blake geomagnetic excursion (~125 ka) measured in three cores from Ocean Drilling Program (ODP) Site 1062 on the Blake-Bahama Outer Ridge. The Blake excursion has a controversial structure and timing but these cores have a sufficiently high sedimentation rate (~10cm/ka) to allow detailed reconstruction of the field behaviour at this site during the excursion. Palaeomagnetic measurements of the cores reveal rapid transitions (<500 yr) between the contemporary stable normal polarity and a completely reversed state of long duration which spans a stratigraphic interval of 0.7 m. We determine the duration of the reversed state during the Blake excursion using oxygen isotope stratigraphy, combined with 230Th excess measurements to assess variations in the sedimentation rates through the sections of interest. This provides an age and duration for the Blake excursion with greater accuracy and with constrained uncertainty. We date the directional excursion as falling between 129 and 122 ka with a duration for the deviation of 6.5±1.3 kyr. The long duration of this interval and the fully reversed field suggest the existence of a pseudo-stable, reversed dipole field component during the excursion and challenge the idea that excursions are always of short duration.

Magnetostratigraphy of DSDP Leg 73 in the South Atlantic

The main objective of DSDP Leg 73 was to obtain high-quality records of major paleooceanographic events in the South Atlantic. This was achieved by coring six sites on the African plate. The sediments thus recovered span the Cenozoic and five of the six sites proved ideally suited for magnetostratigraphic analysis. The results presented in this paper and elsewhere in this volume constitute the first opportunity to extend the direct correlation of the magnetostratigraphic and biostratigraphic time-scales into the Paleogene in deep-sea cores. The magnetostratigraphic analyses from DSDP Leg 73 sediments are presented in this paper. The correlation of the magnetostratigraphy to the magnetic polarity time-scale provides tight age-depth control for the five sites analyzed, allowing the accurate calculation of sediment accumulation rates. The data presented here represent a remarkable record of the fine-scale polarity history of the Earth's magnetic field. These data place constraints on the interpretation of smallscale marine magnetic anomalies which are modelled equally effectively by field intensity fluctuations as polarity reversals. At least some of the "tiny wiggles" correspond to very short polarity units in the magnetostratigraphic record. By assuming an axial geocentric dipole, the inclination of the time-averaged magnetic field recorded in the sediments can be used to calculate the paleolatitude at which the sediments were deposited. Combining the age and average inclination information available from the magnetostratigraphy, we present paleolatitudes versus time for the Leg 73 drill sites.

Lower Jaramillo polarity transition records from ODP Holes 108-665A and 121-758B

Two records of the geomagnetic polarity transition at the beginning of the Jaramillo Subchron (0.97 Ma) have been obtained from sediments in the equatorial Atlantic (Leg 108, Site 665; 2.95°N, 340.33°E) and Indian (Leg 121, Site 758; 5.38°N, 90.35°E) oceans. Both cores yielded high-quality magnetostratigraphic results; however, the relatively low sedimentation rates, the weak magnetizations, and complex demagnetization behavior of some transitional samples suggest that the record of the transitional field behavior may be less reliable. In addition, variations in grain size preclude reliable paleointensity determinations although the remanence in both cores is apparently dominated by magnetite. Despite these possible complications, the two cores yield transitional paths that are neither far-sided nor near-sided. Together with published records that meet minimum reliability standards, the two equatorial records presented here suggest that the lower Jaramillo transitional field morphology was significantly nonaxisymmetric. The mean normal and reversed inclinations from both cores deviate from the inclination expected from a geocentric axial dipole, as noted in virtually all marine sediment cores. The observed inclinations provide further support for a polarity-dependent nondipole contribution to the time-averaged field.