Thermal Relaxation Rate Research Articles

Analysis of static Wilson line correlators from lattice QCD at finite temperature with T-matrix approach

The thermodynamic T-matrix approach is used to study Wilson line correlators (WLCs) for a static quark-antiquark pair in the quark-gluon plasma (QGP). Selfconsistent results that incorporate constraints from the QGP equation of state can approximately reproduce WLCs computed in 2+1-flavor lattice-QCD (lQCD), provided the input potential exhibits less screening than in previous studies. Utilizing the updated potential to calculate pertinent heavylight T-matrices we evaluate thermal relaxation rates of heavy quarks in the QGP. We find a more pronounced temperature dependence for low-momentum quarks than in our previous results (with larger screening), which turns into a weaker temperature dependence of the (temperature-scaled) spatial diffusion coefficient, in fair agreement with the most recent lQCD data.

In Situ Photoisomerization of an Azobenzene-Based Triple Helicate with a Prolonged Thermal Relaxation Time.

The phosphate-coordination triple helicates A2 L3 (A=anion) with azobenzene-spaced bis-bis(urea) ligands (L) have proven to undergo a rare in situ photoisomerization (without disassembly of the structure) rather than the typically known, stepwise "disassembly-isomerization-reassembly" process. This is enabled by the structural self-adaptability of the "aniono" assembly arising from multiple relatively weak and flexible hydrogen bonds between the phosphate anion and bis(urea) units. Notably, the Z→E thermal relaxation rate of the isomerized azobenzene unit is significantly decreased (up to 20-fold) for the triple helicates compared to the free ligands. Moreover, the binding of chiral guest cations inside the cavity of the Z-isomerized triple helicate can induce optically pure diastereomers, thus demonstrating a new strategy for making light-activated chiroptical materials.

In Situ Photoisomerization of an Azobenzene‐Based Triple Helicate with a Prolonged Thermal Relaxation Time

AbstractThe phosphate‐coordination triple helicates A2L3 (A=anion) with azobenzene‐spaced bis‐bis(urea) ligands (L) have proven to undergo a rare in situ photoisomerization (without disassembly of the structure) rather than the typically known, stepwise “disassembly‐isomerization‐reassembly” process. This is enabled by the structural self‐adaptability of the “aniono” assembly arising from multiple relatively weak and flexible hydrogen bonds between the phosphate anion and bis(urea) units. Notably, the Z→E thermal relaxation rate of the isomerized azobenzene unit is significantly decreased (up to 20‐fold) for the triple helicates compared to the free ligands. Moreover, the binding of chiral guest cations inside the cavity of the Z‐isomerized triple helicate can induce optically pure diastereomers, thus demonstrating a new strategy for making light‐activated chiroptical materials.

Microresonator Effective Thermal Parameters Definition via Thermal Modes Decomposition

High-Q optical microresonators are particularly efficient practical tools of modern applied optics and photonics. Using them, one inevitably faces the problem of thermal effects. Accurate determination of effective thermal parameters of high-Q microresonators (effective thermal relaxation rate and optical absorption rate) is of particular importance for developing microresonator-based devices. Our investigation looks into diverse methodologies to estimate these effective parameters for such systems, ultimately revealing a divergence between the commonly employed simplified model, the direct numerical approach, and classical analytical formulas. We introduce a novel approach to calculate effective parameters based on the decomposition of the thermal field into microresonator thermal modes, which inherently considers the intricate geometry and material anisotropy inherent in microresonators, as well as the influence of external conditions. The method for the accurate determination of the effective thermal parameters of the microresonator for corresponding thermal modes is developed. As a result of applying this method, we modified the classical approach for the simulation of thermal effects in optical microresonators for better agreement with the numerical simulations. By accounting for the complexities of microresonator shapes, material properties, and external factors, our proposed method contributes to a more accurate understanding of thermal dynamics and enhances the predictive capabilities of simulations for these systems. We demonstrated the application of this method on the example of integrated microring resonators, but it can be used to analyze thermal effects in other microresonator platforms.

Synthesis and anticancer profile of novel FTY720 analogues with azobenzene frameworks

A short synthetic route towards novel cytotoxic FTY720 analogues bearing a variously substituted azobenzene unit was developed. The target compounds were constructed either via a Wittig olefination or Mills reaction as the key processes. Preliminary biological screening revealed the antiproliferative activity of several newly synthesised derivatives against Jurkat, HeLa and HCT-116 cells to be quite promising, comparable or higher than the potency of cisplatin (Brinkmann et al., 2010) [1]. The structure-activity relationship showed that a loss of the alkyl side chain on the azobenzene core or its substitution with hydroxymethyl moiety seem to be detrimental for the resulting cytotoxic profile in this series of derivatives. To probe the photochromic properties of the final derivatives, the reversible E/Z isomerisation and thermal relaxation rate were determined.

Augmented Non‐LTE Parameterization of NO Infrared Radiative Cooling Rates

AbstractParameterizations of NO cooling rates in thermospheric models have not changed substantially since the work of Kockarts (1980, https://doi.org/10.1029/GL007i002p0013). We investigate three areas to augment the standard parameterization. The first focuses on cooling‐rate contributions from the first NO “hot band.” Arguments concerning the difficulty or irrelevance of parameterizing hot‐band rates are addressed and either refuted or clarified. Parameterized hot‐band cooling peaks during periods of high solar activity, contributing up to 10%–15% additional cooling, in agreement with published line‐by‐line calculations. The second focuses on collisional NO‐O quenching rates. Recent theoretical calculations predict temperature‐dependent rates similar to those seen in collisional CO2‐O quenching rates. Yet available measurements of NO‐O quenching rates do not reveal clear temperature trends. Quenching rates parameterized with and without temperature dependence produce substantially different thermospheric cooling rates. Further research is needed to resolve these discrepancies. The third involves a linearization of parameterized NO cooling rates around a prescribed state, yielding thermal damping rates for use in parameterizations of subgrid‐scale dynamics. Thermal relaxation rates peak at up to 2 days−1 near 140 km, where they are competitive with corresponding rates due to viscous thermal conduction, consistent with the imputed role of NO in regulating thermospheric climate in response to extraterrestrial energy inputs.

Fabrication and characterization of NbN/(TaN/NbN) N stacked Josephson junctions

In this work, we present a detailed study of the electrical properties of stacked NbN/(TaN/NbN) N Josephson junctions. Cross-sectional scanning transmission electron microscopy analysis of the 5-stacked junction shows that the multilayer interface is very flat, each barrier has the same thickness, and the sidewalls of the junctions are nearly perpendicular to the substrate. Stacked junctions of different sizes and stacking numbers all have only one transition in their current–voltage curves. This indicates that the critical currents of the junctions in the stacked junctions are almost the same, showing the stability and repeatability of the multilayer fabrication and etching process. At 4.2 K, the 4-stacked junction shows excellent Josephson properties with characteristic voltage V c of 3.54 mV, which is about four times the 0.88 mV of the single junction. The temperature dependence of critical current density J c and V c of the stacked junction with N = 1, 2, 4 were measured, all of which can be fitted with dirty-limit theory. Stacked junctions with larger V c or more stacked layers can be achieved by optimizing electrode and barrier thickness, barrier resistivity, and thermal relaxation rate, etc.

ARGET ATRP of Methyl Acrylate and Methyl Methacrylate with Diazocine-Derived Initiators

Diazocine-functionalized initiators for atom transfer radical polymerization (ATRP) were synthesized and tested for their efficiency in controlled radical polymerizations of methyl acrylate and methacrylate under reaction conditions for activators regenerated by electron transfer (ARGET). The α-bromoisobutyl condensates of anilide and benzyloxycarbonate required high amounts of reducing agents and catalysts for the initiation. On the other hand, violet light irradiation during ATRP caused severe retardation or termination during initiation of the anilide compound, in contrast to the previously reported photoinduced initiation under otherwise very similar conditions. The final linear elastomers obtained from optimized polymerization kinetics responded to light irradiation of 405 and 525 nm wavelengths by Z/E photoisomerization of diazocine in both solution and in the solid state. The E → Z thermal relaxation rate was highly influenced by electronic effects on the diazocine ring, the solvent, and the polymer matrix in the solid state. Our polymers find potential use as photonic materials in ultraviolet light sensors and optical waveguides.

Cover Feature: Fine‐Tuning the Thermal Relaxation Dynamics of Indigo‐Based Photoswitches Using Selective Non‐Covalent Interactions Without Chemical Modification (ChemPhotoChem 4/2022)

The Cover Feature shows a molecular complex formed between the Z-isomer of an indigo-based photoswitch and a lithium cation. The formation of this complex stabilizes the Z-isomer and slows the thermal relaxation rate of this photoswitch. In contrast, the uncomplexed molecules have a faster relaxation rate, as shown by the motion blur. Cover image designed by Julie Liu (SIAIS, ShanghaiTech University). More information can be found in the Research Article by Bo Qiao and co-workers.

Fine‐Tuning the Thermal Relaxation Dynamics of Indigo‐Based Photoswitches Using Selective Non‐Covalent Interactions Without Chemical Modification

AbstractUnderstanding the thermal relaxation dynamics of photoswitches is of crucial importance when considering application scenarios. Strategies for regulating the thermal relaxation rates of photoswitches have been mostly limited to modifying the chemical structures. Herein we demonstrate a complementary method of manipulating the thermal relaxation rate of indigo‐based photoswitches that does not require chemical modification. We used indigo‐based photoswitches in aprotic solvents as a model system to demonstrate this strategy. Our method creates a deactivated pathway that extends the thermal relaxation half‐life by selectively stabilizing the parent structure of the metastable Z‐isomer via non‐covalent interaction. In addition, by establishing a quantitative kinetic model, we showed that controlling the strength of such selective stabilization enables fine‐tuning of the thermal relaxation rates to precisely access to targeted values.

Quantum dynamics simulations of the thermal and light-induced high-spin to low-spin relaxation in Fe(bpy)3 and Fe(mtz)6.

First row transition metal complexes with d4 to d7 electronic configurations exhibit spin-crossover (SCO), which can be induced by external stimuli, such as temperature, pressure and light. The low-spin to high-spin transition has been widely studied, but very little is known about the reverse process. Here, we present a theoretical study of thermal and light-induced high-to-low spin crossover in prototypical Fe(II) complexes. The lifetime of the high-spin state in the thermal process is determined using Fermi's golden rule. With this methodology, we have accurately computed the transfer rate of the HS state thermal relaxation at several time scales (from sub-nanosecond to a few seconds) in two different iron complexes. The use of quasi-degenerate perturbation theory (QDPT2) in the analysis of the LS-HS spin-orbit coupling has allowed us to identify 3T1 as the main intermediate state coupling the LS and HS states. The light-induced process has been studied using wavepacket quantum dynamics along the main vibrational coordinates (one symmetric and two asymmetric Fe-N stretchings). The study suggests that after the initial excitation from the 5T2g to the 5Eg state, the population is transferred back to a vibrationally hot 5T2g state, from which a small amount of the population is transferred to the 1A1g state via the intermediate 3T1g. Most of the population remains trapped in the HS state at the time scale of the simulation.

The role of cysteine residues in the allosteric modulation of the chromophore phototransformations of biphotochromic fluorescent protein SAASoti

Biphotochromic fluorescent protein SAASoti contains five cysteine residues in its sequence and a V127T point mutation transforms it to the monomeric form, mSAASoti. These cysteine residues are located far from the chromophore and might control its properties only allosterically. The influence of individual, double and triple cysteine substitutions of mSAASoti on fluorescent parameters and phototransformation reactions (irreversible green-to-red photoconversion and reversible photoswitching) is studied. A set of mSAASoti mutant forms (C21N, C117S, C71V, C105V, C175A, C21N/C71V, C21N/C175A, C21N/C71G/C175A) is obtained by site-directed mutagenesis. We demonstrate that the C21N variant exists in a monomeric form up to high concentrations, the C71V substitution accelerates photoconversion to the red form and the C105V variant has the maximum photoswitching rate. All C175A-containing variants demonstrate different photoswitching kinetics and decreased photostability during subsequent switching cycles compared with other considered systems. Classical molecular dynamic simulations reveal that the F177 side chain located in the vicinity of the chromophore is considerably more flexible in the mSAASoti compared with its C175A variant. This might be the explanation of the experimentally observed slowdown the thermal relaxation rate, i.e., trans–cis isomerization of the chromophore in mSAASoti upon C175A substitution.

Stabilization of thermally unstable photoisomers of pyridinium-functionalized hemithioindigo switches by host-guest complexation

Pyridine-functionalized hemithioindigo photoswitches (Z)-6-(Z)-8 were obtained by an aldol condensation of benzothiophenone 5 with the appropriate pyridinecarbaldehyde. These compounds were methylated with methyl iodide or methyl triflate to obtain pyridinium-functionalized hemithioindigo photoswitches (Z)-2-(Z)-4. The resulting compounds (Z)-2-(Z)-4 and (Z)-6-(Z)-8 could be isomerized to the (E)-isomer with light of λ = 470 nm, with relative abundances of the photoisomers up to 96%. All photoswitches except (Z)-2 could be isomerized back to the (Z)-state with light of longer wavelengths. For (Z)-2 this process of adopting a new photostationary state was slower compared to the thermal relaxation. Switches (Z)-2-(Z)-4 were capable of binding in a porphyrin cage host (H21) with association constants that increased with the distance between the positive charge and the central double bond of the switch: ((Z)-2 < (Z)-3 < (Z)-4). As a result of the complexation with H21 the thermal relaxation rate of (E) → (Z) isomerization decreased up to 3-fold.

The Sandwich Mode for Vertical Shear Instability in Protoplanetary Disks

Abstract Turbulence has a profound impact on the evolution of gas and dust in protoplanetary disks (PPDs), from driving the collisions and the diffusion of dust grains, to the concentration of pebbles in giant vortices, thus, facilitating planetesimal formation. The vertical shear instability (VSI) is a hydrodynamic mechanism, operating in PPDs if the local rate of thermal relaxation is high enough. Previous studies of the VSI have, however, relied on the assumption of constant cooling rates, or neglected the finite coupling time between the gas particles and the dust grains. Here, we present the results of hydrodynamic simulations of PPDs with the PLUTO code that include a more realistic thermal relaxation prescription, which enables us to study the VSI in the optically thick and optically thin parts of the disk under consideration of the thermal dust-gas coupling. We show the VSI to cause turbulence even in the optically thick inner regions of PPDs in our two- and three-dimensional simulations. The collisional decoupling of dust and gas particles in the upper atmosphere and the correspondingly inefficient thermal relaxation rates lead to the damping of the VSI turbulence. Long-lived anticyclonic vortices form in our three-dimensional simulation. These structures emerge from the turbulence in the VSI-active layer, persist over hundreds of orbits and extend vertically over the whole extent of the turbulent region. We conclude that the VSI leads to turbulence and the formation of long-lived dust traps within ±3 pressure scale heights distance from the disk midplane.

Mesoproterozoic thermal evolution of the northern Gawler Craton from 40Ar/39Ar geochronology

Previous thermochronology studies of the northern Gawler Craton have interpreted cooling from mid-crustal temperatures in two phases; either cooling subsequent to a c. 1610–1580 Ma event or over the interval c. 1460–1440 Ma, however the extent and the significance of these ages has been uncertain. We have obtained nine new 40Ar/39Ar thermochronological dates on igneous and metamorphic rocks from drill hole samples across the region. The new data show that different fault-bound blocks have different thermal histories, and that cooling to below biotite closure to argon diffusion over the interval c. 1460–1415 Ma was widespread across the region. Arrhenius data from step heating experiments in this study yield closure temperature estimates for biotite samples that range from 436 to 310 °C. Cooling rates ranging from 3 to 5 °C/Myr are widespread across the region, with one block having slightly faster cooling, up to 14 °C/Myr. These rates suggest a combination of cooling related to thermal relaxation and modest erosion rates, with faster cooled zones likely resulting from moderate degrees of active exhumation along shear zone systems. This cooling may be linked to early stages of break-up of the Nuna supercontinent as c. 1460–1415 Ma tectonic activity is also documented across many terranes of the Nuna supercontinent including the Terre Adelie Craton in Antarctica and terranes of Laurentia.

Comparing Relaxation Mechanisms in Quantum and Classical Transverse-Field Annealing

Annealing schedule control provides new opportunities to better understand the manner and mechanisms by which putative quantum annealers operate. By appropriately modifying the annealing schedule to include a pause (keeping the Hamiltonian fixed) for a period of time, we show it is possible to more directly probe the dissipative dynamics of the system at intermediate points along the anneal and examine thermal relaxation rates, for example, by observing the re-population of the ground state after the minimum spectral gap. We provide a detailed comparison of experiments from a D-Wave device, simulations of the quantum adiabatic master equation and a classical analogue of quantum annealing, spin-vector Monte Carlo, and we observe qualitative agreement, showing that the characteristic increase in success probability when pausing is not a uniquely quantum phenomena. We find that the relaxation in our system is dominated by a single time-scale, which allows us to give a simple condition for when we can expect pausing to improve the time-to-solution, the relevant metric for classical optimization. Finally, we also explore in simulation the role of temperature whilst pausing as a means to better distinguish quantum and classical models of quantum annealers.

The C(3P) + O2(3Σg-) → CO2 ↔ CO(1Σ+) + O(1D)/O(3P) reaction: thermal and vibrational relaxation rates from 15 K to 20 000 K.

Thermal rates for the C(3P) + O2(3Σg−) ↔ CO(1Σ+)+ O(1D)/O(3P) reaction are investigated over a wide temperature range based on quasi classical trajectory (QCT) simulations on 3-dimensional, reactive potential energy surfaces (PESs) for the 1A′, (2)1A′, 1A′′, 3A′ and 3A′′ states. These five states are the energetically low-lying states of CO2 and their PESs are computed at the MRCISD+Q/aug-cc-pVTZ level of theory using a state-average CASSCF reference wave function. Analysis of the different electronic states for the CO2 → CO + O dissociation channel rationalizes the topography of this region of the PESs. The forward rates from QCT simulations match measurements between 15 K and 295 K whereas the equilibrium constant determined from the forward and reverse rates is consistent with that derived from statistical mechanics at high temperature. Vibrational relaxation, O + CO(ν = 1,2) → O + CO(ν = 0), is found to involve both, non-reactive and reactive processes. The contact time required for vibrational relaxation to take place is τ ≥ 150 fs for non-reacting and τ ≥ 330 fs for reacting (oxygen atom exchange) trajectories and the two processes are shown to probe different parts of the global potential energy surface. In agreement with experiments, low collision energy reactions for the C(3P) + O2(3Σg−, ν = 0) → CO(1Σ+) + O(1D) lead to CO(1Σ+, ν′ = 17) with an onset at Ec ∼ 0.15 eV, dominated by the 1A′ surface with contributions from the 3A′ surface. Finally, the barrier for the COA(1Σ+) + OB(3P) → COB(1Σ+) + OA(3P) atom exchange reaction on the 3A′ PES yields a barrier of ∼7 kcal mol−1 (0.300 eV), consistent with an experimentally reported value of 6.9 kcal mol−1 (0.299 eV).

Transport coefficients of nucleon neutron star cores for various nuclear interactions within the Brueckner-Hartree-Fock approach

We consider the thermal conductivity, shear viscosity, and momentum relaxation rates in the nucleon cores of the neutron stars. We study how the choice of the nuclear interaction and the model for three-body forces may affect these transport coefficients calculated within the Brueckner-Hartree-Fock many-body nuclear theory. We find that at relatively large densities the model dependence of the results is substantial. In addition we provide the analytical approximations which allow to incorporate our results in practical simulations.

Polysubstituted 5‐Phenylazopyrimidines: Extremely Fast Non‐ionic Photochromic Oscillators

Photochromic systems with an ultrahigh rate of thermal relaxation are highly desirable for the development of new efficient photochromic oscillators. Based on DFT calculations, we designed a series of 5-phenylazopyrimidines with strong push-pull character in silico and observed very low energy barriers for the thermal (Z)-to-(E) isomerization. The structure of the (Z)-isomer of the slowest isomerizing derivative in the series was confirmed by NMR analysis with in situ irradiation at low temperature. The substituents can tune the lifetime of thermal back isomerization from hundreds of microseconds to several nanoseconds (8 orders of magnitude). The photoswitching parameters were extracted from transient absorption techniques and a dominant rotation mechanism of the (Z)-to-(E) thermal fading was proposed based on DFT calculations.

Polysubstituted 5‐Phenylazopyrimidines: Extremely Fast Non‐ionic Photochromic Oscillators

AbstractPhotochromic systems with an ultrahigh rate of thermal relaxation are highly desirable for the development of new efficient photochromic oscillators. Based on DFT calculations, we designed a series of 5‐phenylazopyrimidines with strong push–pull character in silico and observed very low energy barriers for the thermal (Z)‐to‐(E) isomerization. The structure of the (Z)‐isomer of the slowest isomerizing derivative in the series was confirmed by NMR analysis with in situ irradiation at low temperature. The substituents can tune the lifetime of thermal back isomerization from hundreds of microseconds to several nanoseconds (8 orders of magnitude). The photoswitching parameters were extracted from transient absorption techniques and a dominant rotation mechanism of the (Z)‐to‐(E) thermal fading was proposed based on DFT calculations.