Understanding defect formation during laser additive manufacturing (LAM) of virgin, stored, and reused powders is crucial for the production of high quality additively manufactured parts. We ...investigate the effects of powder oxidation on the molten pool dynamics and defect formation during LAM. We compare virgin and oxidised Invar 36 powder under overhang and layer-by-layer build conditions using in situ and operando X-ray Imaging. The oxygen content of the oxidised powder was found to be ca. 6 times greater (0.343 wt.%) than the virgin powder (0.057 wt.%). During LAM, the powder oxide is entrained into the molten pool, altering the Marangoni convection from an inward centrifugal to an outward centripetal flow. We hypothesise that the oxide promotes pore nucleation, stabilisation, and growth. We observe that spatter occurs more frequently under overhang conditions compared to layer-by-layer conditions. Droplet spatter can be formed by indirect laser-driven gas expansion and by the laser-induced metal vapour at the melt surface. Under layer-by-layer build conditions, laser re-melting reduces the pore size distribution and number density either by promoting gas release from keyholing or by inducing liquid flow, partially or completely filling pre-existing pores. We also observe that pores residing at the track surface can burst during laser re-melting, resulting in either formation of droplet spatter and an open pore or healing of the pore via Marangoni flow. This study confirms that excessive oxygen in the powder feedstock may cause defect formation in LAM.
Using a laser additive manufacturing process replicator with in situ and operando X-ray imaging (a) permits capturing the formation of (b) porosity and (c) spatter during laser-matter interaction. In addition, we performed post mortem X-ray computed tomography analysis (d) reveal two types of pores inside the melt track: (i) open pores and (ii) closed pores. Display omitted
The laser-matter interaction and solidification phenomena associated with laser additive manufacturing (LAM) remain unclear, slowing its process development and optimisation. Here, through in situ ...and operando high-speed synchrotron X-ray imaging, we reveal the underlying physical phenomena during the deposition of the first and second layer melt tracks. We show that the laser-induced gas/vapour jet promotes the formation of melt tracks and denuded zones via spattering (at a velocity of 1 m s
). We also uncover mechanisms of pore migration by Marangoni-driven flow (recirculating at a velocity of 0.4 m s
), pore dissolution and dispersion by laser re-melting. We develop a mechanism map for predicting the evolution of melt features, changes in melt track morphology from a continuous hemi-cylindrical track to disconnected beads with decreasing linear energy density and improved molten pool wetting with increasing laser power. Our results clarify aspects of the physics behind LAM, which are critical for its development.
Electron transfer (ET) from donor to acceptor is often mediated by nuclear-electronic (vibronic) interactions in molecular bridges. Using an ultrafast electronic-vibrationalvibrational ...pulse-sequence, we demonstrate how the outcome of light-induced ET can be radically altered by mode-specific infrared (IR) excitation of vibrations that are coupled to the ET pathway. Picosecond narrow-band IR excitation of high-frequency bridge vibrations in an electronically excited covalent trans-acetylide platinum(II) donor-bridge-acceptor system in solution alters both the dynamics and the yields of competing ET pathways, completely switching a charge separation pathway off. These results offer a step toward quantum control of chemical reactivity by IR excitation.
In polymeric semiconductors, charge carriers are polarons, which means that the excess charge deforms the molecular structure of the polymer chain that hosts it. This results in distinctive ...signatures in the vibrational modes of the polymer. Here, we probe polaron photogeneration dynamics at polymer:fullerene heterojunctions by monitoring its time-resolved resonance-Raman spectrum following ultrafast photoexcitation. We conclude that polarons emerge within 300 fs. Surprisingly, further structural evolution on ≲ 50-ps timescales is modest, indicating that the polymer conformation hosting nascent polarons is not significantly different from that near equilibrium. We interpret this as suggestive that charges are free from their mutual Coulomb potential because we would expect rich vibrational dynamics associated with charge-pair relaxation. We address current debates on the photocarrier generation mechanism at molecular heterojunctions, and our work is, to our knowledge, the first direct probe of molecular conformation dynamics during this fundamentally important process in these materials.
The ability of carboxylate groups to promote the direct functionalization of C–H bonds in organic compounds is unquestionably one of the most important discoveries in modern chemical synthesis. ...Extensive computational studies have indicated that this process proceeds through the deprotonation of a metal-coordinated C–H bond by the basic carboxylate, yet experimental validation of these predicted mechanistic pathways is limited and fraught with difficulty, mainly as rapid proton transfer is frequently obscured in ensemble measures in multistep reactions (i.e., a catalytic cycle consisting of several steps). In this paper, we describe a strategy to experimentally observe the microscopic reverse of the key C–H bond activation step underpinning functionalization processes (viz. M–C bond protonation). This has been achieved by utilizing photochemical activation of the thermally robust precursor Mn(ppy)(CO)4 (ppy = metalated 2-phenylpyridine) in neat acetic acid. Time-resolved infrared spectroscopy on the picosecond–millisecond time scale allows direct observation of the states involved in the proton transfer from the acetic acid to the cyclometalated ligand, providing direct experimental evidence for the computationally predicted reaction pathways. The power of this approach to probe the mechanistic pathways in transition-metal-catalyzed reactions is demonstrated through experiments performed in toluene solution in the presence of PhC2H and HOAc. These allowed for the observation of sequential displacement of the metal-bound solvent by the alkyne, C–C bond formation though insertion in the Mn–C bond, and a slower protonation step by HOAc to generate the product of a Mn(I)-catalyzed C–H bond functionalization reaction.
Nuclear-electronic (vibronic) coupling is increasingly recognized as a mechanism of major importance in controlling the light-induced function of molecular systems. It was recently shown that ...infrared light excitation of intramolecular vibrations can radically change the efficiency of electron transfer, a fundamental chemical process. We now extend and generalize the understanding of this phenomenon by probing and perturbing vibronic coupling in several molecules in solution. In the experiments an ultrafast electronic-vibrational pulse sequence is applied to a range of donor-bridge-acceptor Pt(II) trans-acetylide assemblies, for which infrared excitation of selected bridge vibrations during ultraviolet-initiated charge separation alters the yields of light-induced product states. The experiments, augmented by quantum chemical calculations, reveal a complex combination of vibronic mechanisms responsible for the observed changes in electron transfer rates and pathways. The study raises new fundamental questions about the function of vibrational processes immediately following charge transfer photoexcitation, and highlights the molecular features necessary for external vibronic control of excited-state processes.
Ultrafast electron transfer in condensed-phase molecular systems is often strongly coupled to intramolecular vibrations that can promote, suppress and direct electronic processes. Recent experiments ...exploring this phenomenon proved that light-induced electron transfer can be strongly modulated by vibrational excitation, suggesting a new avenue for active control over molecular function. Here, we achieve the first example of such explicit vibrational control through judicious design of a Pt(II)-acetylide charge-transfer donor-bridge-acceptor-bridge-donor 'fork' system: asymmetric
C isotopic labelling of one of the two -C≡C- bridges makes the two parallel and otherwise identical donor→acceptor electron-transfer pathways structurally distinct, enabling independent vibrational perturbation of either. Applying an ultrafast UV
(excitation)-IR
(perturbation)-IR
(monitoring) pulse sequence, we show that the pathway that is vibrationally perturbed during UV-induced electron transfer is dramatically slowed down compared to its unperturbed counterpart. One can thus choose the dominant electron transfer pathway. The findings deliver a new opportunity for precise perturbative control of electronic energy propagation in molecular devices.
Ultrafast electron transfer (ET) processes are important primary steps in natural and artificial photosynthesis, as well as in molecular electronic/photonic devices. In biological systems, ET often ...occurs surprisingly fast over long distances of several tens of angströms. Laser-pulse irradiation is conveniently used to generate strongly oxidizing (or reducing) excited states whose reactions are then studied by time-resolved spectroscopic techniques. While photoluminescence decay and UV–vis absorption supply precise kinetics data, time-resolved infrared absorption (TRIR) and Raman-based spectroscopies have the advantage of providing additional structural information and monitoring vibrational energy flows and dissipation, as well as medium relaxation, that accompany ultrafast ET. We will discuss three cases of photoinduced ET involving the ReI(CO)3(N,N) moiety (N,N = polypyridine) that occur much faster than would be expected from ET theories. Re(4-N-methylpyridinium-pyridine)(CO)3(N,N)2+ represents a case of excited-state picosecond ET between two different ligands that remains ultrafast even in slow-relaxing solvents, beating the adiabatic limit. This is caused by vibrational/solvational excitation of the precursor state and participation of high-frequency quantum modes in barrier crossing. The case of Re–tryptophan assemblies demonstrates that excited-state Trp → *ReII ET is accelerated from nanoseconds to picoseconds when the ReI(CO)3(N,N) chromophore is appended to a protein, close to a tryptophan residue. TRIR in combination with DFT calculations and structural studies reveals an interaction between the N,N ligand and the tryptophan indole. It results in partial electronic delocalization in the precursor excited state and likely contributes to the ultrafast ET rate. Long-lived vibrational/solvational excitation of the protein ReI(CO)3(N,N)···Trp moiety, documented by dynamic IR band shifts, could be another accelerating factor. The last discussed process, back-ET in a porphyrin–ReI(CO)3(N,N) dyad, demonstrates that formation of a hot product accelerates highly exergonic ET in the Marcus inverted region. Overall, it follows that ET can be accelerated by enhancing the electronic interaction and by vibrational excitation of the reacting system and its medium, stressing the importance of quantum nuclear dynamics in ET reactivity. These effects are experimentally accessible by time-resolved vibrational spectroscopies (IR, Raman) in combination with quantum chemical calculations. It is suggested that structural dynamics play different mechanistic roles in light-triggered ET involving electronically excited donors or acceptors than in ground-state processes. While TRIR spectroscopy is well suitable to elucidate ET processes on a molecular-level, transient 2D-IR techniques combining optical and two IR (or terahertz) laser pulses present future opportunities for investigating, driving, and controlling ET.
Femto- to picosecond excited-state dynamics of the complexes Re(L)(CO)3(N,N) n (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n = 1+) were investigated using fluorescence ...up-conversion, transient absorption in the 650−285 nm range (using broad-band UV probe pulses around 300 nm) and picosecond time-resolved IR (TRIR) spectroscopy in the region of CO stretching vibrations. Optically populated singlet charge-transfer (CT) state(s) undergo femtosecond intersystem crossing to at least two hot triplet states with a rate that is faster in Cl (∼100 fs)−1 than in imidazole (∼150 fs)−1 complexes but essentially independent of the N,N ligand. TRIR spectra indicate the presence of two long-lived triplet states that are populated simultaneously and equilibrate in a few picoseconds. The minor state accounts for less than 20% of the relaxed excited population. UV−vis transient spectra were assigned using open-shell time-dependent density functional theory calculations on the lowest triplet CT state. Visible excited-state absorption originates mostly from mixed L;N,N•− → ReII ligand-to-metal CT transitions. Excited bpy complexes show the characteristic sharp near-UV band (Cl, 373 nm; imH, 365 nm) due to two predominantly ππ*(bpy•−) transitions. For phen and dmp, the UV excited-state absorption occurs at ∼305 nm, originating from a series of mixed ππ* and Re → CO;N,N•− MLCT transitions. UV−vis transient absorption features exhibit small intensity- and band-shape changes occurring with several lifetimes in the 1−5 ps range, while TRIR bands show small intensity changes (≤5 ps) and shifts (∼1 and 6−10 ps) to higher wavenumbers. These spectral changes are attributable to convoluted electronic and vibrational relaxation steps and equilibration between the two lowest triplets. Still slower changes (≥15 ps), manifested mostly by the excited-state UV band, probably involve local-solvent restructuring. Implications of the observed excited-state behavior for the development and use of Re-based sensitizers and probes are discussed.
Abstract
We report on an ultrafast infrared optical parametric chirped-pulse amplifier (OPCPA), pumped by a 200-W thin-disk Yb-based regenerative amplifier at a repetition rate of 100 kHz. The OPCPA ...is tunable in the spectral range 1.4–3.9
$$\upmu $$
μ
m, generating up to 23 W of < 100-fs signal and 13 W of < 200-fs idler pulses for infrared spectroscopy, with additional spectral filtering capabilities for Raman spectroscopy. The OPCPA can also yield 19 W of 49-fs 1.75-
$$\upmu $$
μ
m signal or 5 W of 62-fs 2.8-
$$\upmu $$
μ
m idler pulses with active carrier-to-envelope-phase (CEP) stabilisation for high-harmonic generation (HHG). We illustrate the versatility of the laser design, catering to various experimental requirements for probing ultrafast science.
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