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We measure high order harmonics from the molecule SF6 over a large range of phase matching conditions and observe several features in the harmonics that are largely independent of such macroscopic conditions. The experimental data are then compared to the quantitative rescattering theory for the generation of harmonics from three orbitals. With this comparison, we are able to assign spectroscopic features in the harmonics to contributions from 1t1g (HOMO) and 5t1u (HOMO-1) orbitals.

We measure high order harmonics from the molecule SF6 over a large range of phase matching conditions and observe several features in the harmonics that are largely independent of such macroscopic conditions. The experimental data are then compared to the quantitative rescattering theory for the generation of harmonics from three orbitals. With this comparison, we are able to assign spectroscopic features in the harmonics to contributions from 1t1g (HOMO) and 5t1u (HOMO-1) orbitals. [ABSTRACT FROM AUTHOR]

The XUV field emitted by impulsively aligned ethylene molecules during high-order harmonic generation is retrieved as a function of molecular orientation. The results can be ascribed to multielectron contributions to the harmonic emission.

Excitation of iron pentacarbonyl [Fe(CO) 5 ], a prototypical photocatalyst, at 266 nm causes the sequential loss of two CO ligands in the gas phase, creating catalytically active, unsaturated iron carbonyls. Despite numerous studies, major aspects of its ultrafast photochemistry remain unresolved because the early excited-state dynamics have so far eluded spectroscopic observation. This has led to the long-held assumption that ultrafast dissociation of gas-phase Fe(CO) 5 proceeds exclusively on the singlet manifold. Herein, we present a combined experimental-theoretical study employing ultrafast extreme ultraviolet transient absorption spectroscopy near the Fe M 2,3 -edge, which features spectral evolution on 100 fs and 3 ps time scales, alongside high-level electronic structure theory, which enables characterization of the molecular geometries and electronic states involved in the ultrafast photodissociation of Fe(CO) 5 . We assign the 100 fs evolution to spectroscopic signatures associated with intertwined structural and electronic dynamics on the singlet metal-centered states during the first CO loss and the 3 ps evolution to the competing dissociation of Fe(CO) 4 along the lowest singlet and triplet surfaces to form Fe(CO) 3 . Calculations of transient spectra in both singlet and triplet states as well as spin-orbit coupling constants along key structural pathways provide evidence for intersystem crossing to the triplet ground state of Fe(CO) 4 . Thus, our work presents the first spectroscopic detection of transient excited states during ultrafast photodissociation of gas-phase Fe(CO) 5 and challenges the long-standing assumption that triplet states do not play a role in the ultrafast dynamics.

Herein, we report on the ultrafast photodissociation of nickel tetracarbonyl-a prototypical metal-ligand model system-at 197 nm. Using mid-infrared transient absorption spectroscopy to probe the bound C≡O stretching modes, we find evidence for the picosecond time scale production of highly vibronically excited nickel dicarbonyl and nickel monocarbonyl, in marked contrast with a prior investigation at 193 nm. Further spectral evolution with a 50 ps time constant suggests an additional dissociation step; the absence of any corresponding growth in signal strongly indicates the production of bare Ni, a heretofore unreported product from single-photon excitation of nickel tetracarbonyl. Thus, by probing the deep UV-induced photodynamics of a prototypical metal carbonyl, this Letter adds time-resolved spectroscopic signatures of these dynamics to the sparse literature at high excitation energies., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In typical carbonyl-containing molecules, bond dissociation events follow initial excitation to nπ C═O * states. However, in acetyl iodide, the iodine atom gives rise to electronic states with mixed nπ C═O * and nσ C-I * character, leading to complex excited-state dynamics, ultimately resulting in dissociation. Using ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy and quantum chemical calculations, we present an investigation of the primary photodissociation dynamics of acetyl iodide via time-resolved spectroscopy of core-to-valence transitions of the I atom after 266 nm excitation. The probed I 4d-to-valence transitions show features that evolve on sub-100-fs time scales, reporting on excited-state wavepacket evolution during dissociation. These features subsequently evolve to yield spectral signatures corresponding to free iodine atoms in their spin-orbit ground and excited states with a branching ratio of 1.1:1 following dissociation of the C-I bond. Calculations of the valence excitation spectrum via equation-of-motion coupled cluster with single and double substitutions (EOM-CCSD) show that initial excited states are of spin-mixed character. From the initially pumped spin-mixed state, we use a combination of time-dependent density functional theory (TDDFT)-driven nonadiabatic ab initio molecular dynamics and EOM-CCSD calculations of the N 4,5 edge to reveal a sharp inflection point in the transient XUV signal that corresponds to rapid C-I homolysis. By examining the molecular orbitals involved in the core-level excitations at and around this inflection point, we are able to piece together a detailed picture of C-I bond photolysis in which d → σ* transitions give way to d → p excitations as the bond dissociates. We also report theoretical predictions of short-lived, weak 4 d → 5 d transitions in acetyl iodide, validated by weak bleaching in the experimental transient XUV spectra. This joint experimental-theoretical effort has thus unraveled the detailed electronic structure and dynamics of a strongly spin-orbit coupled system.

We have measured, analyzed, and simulated the ground state valence photoelectron spectrum, x-ray absorption (XA) spectrum, x-ray photoelectron (XP) spectrum as well as normal and resonant Auger-Meitner electron (AE) spectrum of oxazole at the carbon, oxygen, and nitrogen K-edge in order to understand its electronic structure. Experimental data are compared to theoretical calculations performed at the coupled cluster, restricted active space perturbation theory to second-order and time-dependent density functional levels of theory. We demonstrate (1) that both N and O K-edge XA spectra are sensitive to the amount of dynamical electron correlation included in the theoretical description and (2) that for a complete description of XP spectra, additional orbital correlation and orbital relaxation effects need to be considered. The normal AE spectra are dominated by a singlet excitation channel and well described by theory. The resonant AE spectra, however, are more complicated. While the participator decay channels, dominating at higher kinetic energies, are well described by coupled cluster theory, spectator channels can only be described satisfactorily using a method that combines restricted active space perturbation theory to second order for the bound part and a one-center approximation for the continuum.

Worker polymorphism in ants has evolved repeatedly, with considerable differences in the morphometry of worker subcastes. Such body size differences and especially caste- and subcaste-specific characteristics might significantly influence locomotion. Therefore, we performed a comprehensive locomotion analysis along gradients in both body size and walking speed of Camponotus fellah worker subcastes, and of males, which have rarely been studied to date because of their short life spans associated with mating flights. We provide a detailed description of the morphometry and size differences of C. fellah castes and subcastes and analyse locomotion in the different polymorphic groups in terms of absolute and relative walking speeds (mesosoma lengths per second). Our results reveal that body size and shape affect locomotion behaviour to different extents in the worker subcastes (minor workers, medias, major workers) and in males. Nevertheless, C. fellah ants use the same overall locomotion strategy, with males and major workers reaching considerably lower walking speeds than minors and medias. Body size thus mainly affects walking speed. Minor workers reach the highest relative velocities by high relative stride lengths in combination with large vertical and lateral centre of mass oscillations and clearly higher stride frequencies of up to 25 Hz. Locomotion of males was characterised by clearly lower walking speeds, wider footprint positions, significant phase shifts and a notable dragging of the shorter hind legs. However, general walking parameters of males differed less from those of the female workers than expected as a result of division of labour in the colony., Competing Interests: Competing interests The authors declare no competing or financial interests., (© 2022. Published by The Company of Biologists Ltd.)

While insect locomotion has been intensively studied, there are comparably few studies investigating octopedal walking behaviour, and very little is known about pseudoscorpions in particular. Therefore, we performed an extensive locomotion analysis during forward, backward and upside-down walking in the cosmopolitan pseudoscorpion Chelifer cancroides. During forward locomotion, we observed C. cancroides to freeze locomotion frequently for short time periods. These microstops were barely visible to the naked eye with a duration of 100-200 ms. Our locomotion analysis revealed that C. cancroides performs a statically stable and highly coordinated alternating tetrapod gait during forward and backward walking, with almost complete inversion of the tetrapod schemes, but no rigidly fixed leg coordination during upside-down walks with low walking speeds up to 4 body lengths per second. Highest speeds (up to 17 body lengths per second), mainly achieved by consistent leg coordination and strong phase shifts, were observed during backward locomotion (escape behaviour), whereas forward walking was characterised by lower speeds and phase shifts of ∼10% between two loosely coupled leg groups within one tetrapod. That is, during the movement of one tetrapod group, the last and the third leg are almost synchronous in their swing phases, as are the second and the first leg. A special role of the second leg pair was demonstrated, probably mainly for stability reasons and related to the large pedipalps., Competing Interests: Competing interests The authors declare no competing or financial interests., (© 2022. Published by The Company of Biologists Ltd.)

We employ ultrafast mid-infrared transient absorption spectroscopy to probe the rapid loss of carbonyl ligands from gas-phase nickel tetracarbonyl following ultraviolet photoexcitation at 261 nm. Here, nickel tetracarbonyl undergoes prompt dissociation to produce nickel tricarbonyl in a singlet excited state; this electronically excited tricarbonyl loses another CO group over tens of picoseconds. Our results also suggest the presence of a parallel, concerted dissociation mechanism to produce nickel dicarbonyl in a triplet excited state, which likely dissociates to nickel monocarbonyl. Mechanisms for the formation of these photoproducts in multiple electronic excited states are theoretically predicted with one-dimensional cuts through the potential energy surfaces and computation of spin-orbit coupling constants using equation of motion coupled cluster methods (EOM-CC) and coupled cluster theory with single and double excitations (CCSD). Bond dissociation energies are calculated with CCSD, and anharmonic frequencies of ground and excited state species are computed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT).

Desert ants show a large range of adaptations to their habitats. They can reach extremely high running speeds, for example, to shorten heat stress during foraging trips. It has recently been examined how fast walking speeds are achieved in different desert ant species. It is intriguing in this context that some species exhibit distinct intraspecific size differences. We therefore performed a complete locomotion analysis over the entire size spectrum of the species Cataglyphis bicolor, and we compared this intraspecific dataset with that of the allometrically similar species Cataglyphis albicans. Emphasis was on the allometry of locomotion: we considered the body size of each animal and analysed the data in terms of relative walking speed. Body size was observed to affect walking parameters, gait patterns and phase relationships in terms of absolute walking speed. Unexpectedly, on a relative scale, all ants tended to show the same overall locomotion strategy at low walking speeds, and significant differences occurred only between C. albicans and C. bicolor at high walking speeds. Our analysis revealed that C. bicolor ants use the same overall strategy across all body sizes, with small ants reaching the highest walking speeds (up to 80 body lengths s-1) by increasing their stride length and incorporating aerial phases. By comparison, C. albicans reached high walking speeds mainly by a high synchrony of leg movement, lower swing phase duration and higher stride frequency ranging up to 40 Hz., Competing Interests: Competing interests The authors declare no competing or financial interests., (© 2021. Published by The Company of Biologists Ltd.)

It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. We employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO) 3 within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).

Conformational isomerism plays a crucial role in defining the physical and chemical properties and biological activity of molecules ranging from simple organic compounds to complex biopolymers. However, it is often a significant challenge to differentiate and separate these isomers experimentally as they can easily interconvert due to their low rotational energy barrier. Here, we use the momentum correlation of fragment ions produced after inner-shell photoionization to distinguish conformational isomers of 1,2-dibromoethane (C 2 H 4 Br 2 ). We demonstrate that the three-body breakup channel, C 2 H 4 + + Br + + Br + , contains signatures of both sequential and concerted breakup, which are decoupled to distinguish the geometries of two conformational isomers and to quantify their relative abundance. The sensitivity of our method to quantify these yields is established by measuring the relative abundance change with sample temperature, which agrees well with calculations. Our study paves the way for using Coulomb explosion imaging to track subtle molecular structural changes.

Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S-C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.

We present an experimental technique using orbital angular momentum (OAM) in a fundamental laser field to drive high harmonic generation (HHG). The mixing of beams with different OAM allows us to generate two laser foci tightly spaced which generate harmonics that interfere in the far field. Thus, this technique is an OAM based in situ HHG interferometric spectroscopic method. With this tool, we measure the phase and amplitude of the angle dependent multiorbital HHG emission in molecular nitrogen.

In this work we demonstrate the generation of two intense, ultrafast laser pulses that allow a controlled interferometric measurement of higher harmonic generation pulses with 12.8 attoseconds in resolution (half the atomic unit of time) and a precision as low as 680 zeptoseconds (10 -21 seconds). We create two replicas of a driving femtosecond pulse which share the same optical path except at the focus where they converge to two foci. An attosecond pulse train emerges from each focus through the process of high harmonic generation. The two attosecond pulse trains from each focus interfere in the far field producing a clear interference pattern in the extreme ultraviolet region. By controlling the relative optical phase (carrier envelope phase for pulsed fields) between the two driving laser pulses we are able to actively influence the delay between the pulses and are able to perform very stable and precise pump-probe experiments. Because of the phase shaping operation occurs homogeneously across the entire spatial profile, we effectively create two indistinguishable intense laser pulses or a common path interferometer for attosecond pulses. Commonality across the two beams means that they are extremely stable to environmental and mechanical fluctuations up to a Rayleigh range from the focus. In our opinion this represents an ideal source for homodyne and heterodyne spectroscopic measurements with sub-attosecond precision.

Although significant progress has been made in targeted and immunologic therapeutics for melanoma, many tumors fail to respond, and most eventually progress when treated with the most efficacious targeted combination therapies thus far identified. Therefore, alternative approaches that exploit distinct melanoma phenotypes are necessary to develop new approaches for therapeutic intervention. Tissue microarrays containing human nevi and melanomas were used to evaluate levels of the antioxidant protein thioredoxin reductase 1 (TR1), which was found to increase as a function of disease progression. Melanoma cell lines revealed metabolic differences that correlated with TR1 levels. We used this new insight to design a model treatment strategy that creates a synthetic lethal interaction wherein targeting TR1 sensitizes melanoma to inhibition of glycolytic metabolism, resulting in a decrease in metastases in vivo. This approach holds the promise of a new clinical therapeutic strategy, distinct from oncoprotein inhibition., (© 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Acute rejection (AR) is an important factor for the development of chronic allograft dysfunction following kidney Tx. Identification of patients who would benefit from closer clinical surveillance to allow individual tailoring of immunosuppression and hence reducing the rate of AR is highly desired. Aim of this study was to investigate the association of pre-transplant alloreactivity and frequency of regulatory T cells (T(regs) ) with AR following living-donor kidney Tx. Peripheral blood mononuclear cells were isolated from 40 patients prior to Tx. T-cell alloreactivity against donor and third-party antigen was assessed by proliferative responses in mixed lymphocyte culture and enzyme linked immunospot technique. Pre-transplant frequency of CD4(+) CD25(+) CD127(low) FoxP3(+) T(regs) was determined by flow cytometry. Experimental data were correlated with occurrence of AR. We found that patients with rejection-free (RF) post-Tx courses showed significantly lower pre-transplant alloreactivity to donor antigen compared to individuals with borderline findings (BL) or AR. For RF patients, the proliferative T-cell responses to third-party antigen were significantly higher than for stimulation with donor cells whereas lymphocytes of the AR group showed the inverse pattern. A significantly higher expression of FoxP3 within the CD4(+) CD25(+) CD127(low) subset for RF and BL compared to the AR group was observed. In conclusion, pre-transplant anti-donor alloreactivity and FoxP3 expression within the CD4(+) CD25(+) CD127(low) subpopulation might prove useful to further define the patient's risk for AR., (© 2010 John Wiley & Sons A/S.)

Monoclonal anti-CD25-antibodies are successfully applied in organ transplantation to reduce the incidence of acute graft rejection. However, targeting the CD25 molecule might not only affect activated T-cells but also regulatory T-cells (T(regs)) constitutively expressing the CD4(+)CD25(+)CD127(low)FoxP3(+) phenotype. In this study, we investigated the influence of the anti-CD25-antibody Basiliximab on the frequency of T(regs) early after kidney transplantation comparing individuals receiving/not receiving induction therapy (n = 14 and n = 7). Following Basiliximab administration, a distinct loss of CD4(+)CD25(high) T-cells was observed lasting for at least 6 weeks. This was not accompanied by a disappearance of the entire CD4(+)CD25(+)FoxP3(+) T(regs) but rather a decreased expression density of CD25 on the latter. In addition, a transient rise in CD4(+)CD25(-)FoxP3(+) T-cells was found which expressed the CD127(low) phenotype. Thus, a phenotypic shift of T(regs) from the CD25(+) to the CD25(-) compartment was suggested. This was supported by in vitro findings showing that the disappearance of CD4(+)CD25(high) cells in the presence of Basiliximab was due to down-regulation of CD25 expression meanwhile the suppressive function of these cells was maintained. In conclusion, Basiliximab therapy directly affects CD4(+)CD25(+)CD127(low)FoxP3(+) T(regs) but does not seem to be associated with functional consequences. Thus, it is unlikely that Basiliximab treatment negatively influences strategies involving T(regs) to promote tolerance after organ transplantation.