Short-time Decay Research Articles

Harmonic chain driven by active Rubin bath: transport properties and steady-state correlations

Characterizing the properties of an extended system driven by active reservoirs is a question of increasing importance. Here, we address this question in two steps. We start by investigating the dynamics of a probe particle connected to an ‘active Rubin bath’: a linear chain of overdamped run-and-tumble particles. We derive exact analytical expressions for the effective noise and dissipation kernels, acting on the probe and show that the active nature of the bath leads to a modified fluctuation–dissipation relation. In the next step, we study the properties of an activity-driven system, modelled by a chain of harmonic oscillators connected to two such active reservoirs at the two ends. We show that the system reaches a non-equilibrium stationary state (NESS), remarkably different from that generated due to a thermal gradient. We characterize this NESS by computing the kinetic temperature profile, spatial and temporal velocity correlations of the oscillators, and the average energy current flowing through the system. It turns out that the activity drive leads to the emergence of two characteristic length-scales, proportional to the activities of the reservoirs. Strong signatures of activity are also manifest in the anomalous short-time decay of the velocity autocorrelations. Finally, we find that the energy current shows a non-monotonic dependence on the activity drive and reversal in direction, corroborating previous findings.

Hypocoercivity in Hilbert spaces

The concept of hypocoercivity for linear evolution equations with dissipation is discussed and equivalent characterizations that were developed for the finite-dimensional case are extended to separable Hilbert spaces. Using the concept of a hypocoercivity index, quantitative estimates on the short-time and long-time decay behavior of a hypocoercive system are derived. As a useful tool for analyzing the structural properties, an infinite-dimensional staircase form is also derived and connections to linear systems and control theory are presented. Several examples illustrate the new concepts and the results are applied to the Lorentz kinetic equation.

Micro-Solvation of Propofol in Propylene Glycol-Water Binary Mixtures: Molecular Dynamics Simulation Studies.

The water microstructure around propofol plays a crucial role in controlling their solubility in the binary mixture. The unusual nature of such a water microstructure can influence both translational and reorientational dynamics, as well as the water hydrogen bond network near propofol. We have carried out all-atom molecular dynamics simulations of five different compositions of the propylene glycol (PG)/water binary mixture containing propofol (PFL) molecules to investigate the differential behavior of water microsolvation shells around propofol, which is likely to control the propofol solubility. It is evident from the simulation snapshots for various compositions that the PG at high molecular ratio favors the water cluster and extended chainlike network that percolates within the PG matrix, where the propofol is in the dispersed state. We estimated that the radial distribution function indicates higher ordered water microstructure around propofol for high PG content, as compared to the lower PG content in the PG/water mixture. So, the hydrophilic PG regulates the stability of the water micronetwork around propofol and its solubility in the binary mixture. We observed that the translational and rotational mobility of water belonging to the propofol microsolvation shell is hindered for high PG content and relaxed toward the low PG molecular ratio in the PG/water mixture. It has been noticed that the structural relaxation of the hydrogen bond formed between the propofol and the water molecules present in the propofol microsolvation shell for all five compositions is found to be slower for high PG content and becomes faster on the way to low PG content in the mixture. Simultaneously, we calculated the intermittent residence time correlation function of the water molecules belonging to the microsolvation shell around the propofol for five different compositions and found a faster short time decay followed up with long time components. Again, the origin of such long time decay is primarily from the structural relaxation of the microsolvation shell around the propofol, where the high PG content shows the slower structural relaxation that turns faster as the PG content approaches to the other end of the compositions. So, our studies showed that the slower structural relaxation of the microsolvation shell around propofol for a high PG molecular ratio in the PG/water mixture correlate well with the extensive ordering of the water microstructure and restricted water mobility and facilitates the dissolution process of propofol in the binary mixture.

Effect of Initial Conditions Sampling on Surface Hopping Simulations in the Ultrashort and Picosecond Time Range. Azomethane Photodissociation as a Case Study

We tested the effect of different ways of sampling the initial conditions in surface hopping simulations, with a focus on the initial energy distributions and on the treatment of the zero point energy (ZPE). As a test case, we chose the gas phase photodynamics of azomethane, which features different processes occurring in overlapping time scales: geometry relaxation in the excited state, internal conversion, photoisomerization, and fast and slow dissociation. The simulations, based on a semiempirical method, had a sufficiently long duration (10 ps) to encompass all of the above processes. We tested several variants of methods based on the quantum mechanical (QM) distributions of the nuclear coordinates q and momenta p, which yield, at least on the average over a large sampling set, the correct QM energy, namely the ZPE when starting from the ground vibrational state. We compared the QM samplings with the classical Boltzmann (CB) distribution obtained by a thermostated trajectory, whereby thermal effects are taken into account, but the ZPE is utterly ignored. We found that most QM and CB approaches yield similar results as to short time dynamics and decay lifetimes, whereas the rate of the ground state dissociation reaction CH3NNCH3 → CH3NN + CH3 is sharply affected by the sampling method. With QM samplings a large fraction of trajectories dissociate promply (<1 ps) after decay to the ground state and with rates of the order of 10-1 ps-1 after the first ps. Instead, the CB samplings yield a much smaller fraction of prompt dissociations and much lower rates at long times. We provided evidence that the ZPE "leaks" from high frequency modes to the reactive ones (N-C bond elongations), therefore unphysically increasing the dissociation rates with QM samplings. We show that an effective way to take into account the ZPE and to avoid the "leaking" problem is to add the ZPE to the potential energy surfaces as a function of the most relevant internal coordinates. Then, Boltzmann sampling can be done as usual, so this approach is suitable also for condensed state dynamics. In the tests we present here, the ZPE correction method yields dissociation rates intermediate between QM and uncorrected Boltzmann samplings.

Spectral form factor for free large N gauge theory and strings

We investigate the spectral form factor in two different systems, free large N gauge theories and highly excited string gas. In both cases, after a rapid decay of the spectral form factor at early time, new contributions come in, preventing the spectral form factor from ever becoming exponentially small. We consider U(N) gauge theories with only adjoint matter and compute the spectral form factor using a matrix integral of the thermal holonomy U. The new saddles differ from the early time saddle by preserving certain subgroups of the center symmetry. For a gas of strings, the short time decay of the spectral form factor is governed by the continuous Hagedorn density of states, which can be associated to the thermal winding mode with winding number ±1. We show that the rise of the spectral form factor comes from other winding modes that also carry momentum along the time direction. We speculate on the existence of a family of classical solutions for these string modes, similar to the Horowitz-Polchinski solution.We review a similar problem for black holes. In particular, we examine the Kontsevich-Segal criterion on complex black holes that contribute to the spectral form factor. In the canonical ensemble quantity Z(β + it), the black hole becomes unallowed at t ~ mathcal{O} (β). A way to avoid this is to consider the microcanonical ensemble, where the black hole stays allowable.

AcidoCEST-UTE MRI Reveals an Acidic Microenvironment in Knee Osteoarthritis.

A relationship between an acidic pH in the joints, osteoarthritis (OA), and pain has been previously demonstrated. Acidosis Chemical Exchange Saturation Transfer (acidoCEST) indirectly measures the extracellular pH through the assessment of the exchange of protons between amide groups on iodinated contrast agents and bulk water. It is possible to estimate the extracellular pH in the osteoarthritic joint using acidoCEST MRI. However, conventional MR sequences cannot image deep layers of cartilage, meniscus, ligaments, and other musculoskeletal tissues that present with short echo time and fast signal decay. Ultrashort echo time (UTE) MRI, on the other hand, has been used successfully to image those joint tissues. Here, our goal is to compare the pH measured in the knee joints of volunteers without OA and patients with severe OA using acidoCEST-UTE MRI. Patients without knee OA and patients with severe OA were examined using acidoCEST-UTE MRI and the mean pH of cartilage, meniscus, and fluid was calculated. Additionally, the relationship between the pH measurements and the Knee Injury and Osteoarthritis Outcome Score (KOOS) was investigated. AcidoCEST-UTE MRI can detect significant differences in the pH of knee cartilage, meniscus, and fluid between joints without and with OA, with OA showing lower pH values. In addition, symptoms and knee-joint function become worse at lower pH measurements.

Unraveling the temperature dynamics and hot electron generation in tunable gap-plasmon metasurface absorbers

Abstract Localized plasmons formed in ultrathin metallic nanogaps can lead to robust absorption of incident light. Plasmonic metasurfaces based on this effect can efficiently generate energetic charge carriers, also known as hot electrons, owing to their ability to squeeze and enhance electromagnetic fields in confined subwavelength spaces. However, it is very challenging to accurately identify and quantify the dynamics of hot carriers, mainly due to their ultrafast time decay. Their nonequilibrium temperature response is one of the key factors missing to understand the short time decay and overall transient tunable absorption performance of gap-plasmon metasurfaces. Here, we systematically study the temperature dynamics of hot electrons and their transition into thermal carriers at various timescales from femto to nanoseconds by using the two-temperature model. Additionally, the hot electron temperature and generation rate threshold values are investigated by using a hydrodynamic nonlocal model approach that is more accurate when ultrathin gaps are considered. The derived temperature dependent material properties are used to study the ultrafast transient nonlinear modification in the absorption spectrum before plasmon-induced lattice heating is established leading to efficient tunable nanophotonic absorber designs. We also examine the damage threshold of these plasmonic absorbers under various pulsed laser illuminations, an important quantity to derive the ultimate input intensity limits that can be used in various emerging nonlinear optics and other tunable nanophotonic applications. The presented results elucidate the role of hot electrons in the response of gap-plasmon metasurface absorbers which can be used to design more efficient photocatalysis, photovoltaics, and photodetection devices.

Effects of interactions, structure formation, and polydispersity on the dynamic magnetic susceptibility and magnetic relaxation of ferrofluids

Linear response theory relates the decay of equilibrium magnetisation fluctuations in a ferrofluid to the frequency-dependent response of the magnetisation to a weak ac external magnetic field. The characteristic relaxation times are strongly affected by interactions between the constituent particles. Similarly, the relaxation of an initially magnetised system towards equilibrium in zero field occurs on a range of timescales depending on the structure of the initial state, and the interactions between the particles. In this work, ferrofluids are modelled as colloidal suspensions of spherical particles carrying point dipole moments, and undergoing Brownian motion. Recent theoretical and simulation work on the relaxation and linear response of these model ferrofluids is reviewed, and the effects of interactions, structure formation, and polydispersity on the characteristic time scales are outlined. It is shown that: (i) in monodisperse ferrofluids, the timescale characterising the collective response to weak fields increases with increasing interaction strength and/or concentration; (ii) in monodisperse ferrofluids, the initial, short-time decay is independent of interaction strength, but the asymptotic relaxation time is the same as that characterising the collective response to weak fields; (iii) in the strong-interaction regime, the formation of self-assembled chains and rings introduces additional timescales that vary by orders of magnitude; and (iv) in polydisperse ferrofluids, the instantaneous magnetic relaxation time of each fraction varies in a complex way due to the role of interactions.

Regularizing effect and decay results for a parabolic problem with repulsive superlinear first order terms

We want to analyze both regularizing effect and long, short time decay concerning a class of parabolic equations having first order superlinear terms. The model problem is the following: $$\begin{aligned} {\left\{ \begin{array}{ll} \displaystyle u_t-\text {div }(A(t,x)|\nabla u|^{p-2}\nabla u)=\gamma |\nabla u|^q &{} \text {in}\,\,(0,T)\times \Omega ,\\ u=0 &{}\text {on}\,\,(0,T)\times \partial \Omega ,\\ u(0,x)=u_0(x) &{}\text {in}\,\, \Omega , \end{array}\right. } \end{aligned}$$ where $$\Omega $$ is an open bounded subset of $${{\,\mathrm{{{\mathbb {R}}}}\,}}^N$$ , $$N\ge 2$$ , $$0<T\le \infty $$ , $$1<p<N$$ and $$q<p$$ . We assume that A(t, x) is a coercive, bounded and measurable matrix, the growth rate q of the gradient term is superlinear but still subnatural, $$\gamma $$ is a positive constant, and the initial datum $$u_0$$ is an unbounded function belonging to a well precise Lebesgue space $$L^\sigma (\Omega )$$ for $$\sigma =\sigma (q,p,N)$$ .

Effects of interactions on magnetization relaxation dynamics in ferrofluids.

The dynamics of magnetization relaxation in ferrofluids are studied with statistical-mechanical theory and Brownian dynamics simulations. The particle dipole moments are initially perfectly aligned, and the magnetization is equal to its saturation value. The magnetization is then allowed to decay under zero-field conditions toward its equilibrium value of zero. The time dependence is predicted by solving the Fokker-Planck equation for the one-particle orientational distribution function. Interactions between particles are included by introducing an effective magnetic field acting on a given particle and arising from all of the other particles. Two different approximations are proposed and tested against simulations: a first-order modified mean-field theory and a modified Weiss model. The theory predicts that the short-time decay is characterized by the Brownian rotation time τ_{B}, independent of the interaction strength. At times much longer than τ_{B}, the asymptotic decay time is predicted to grow with increasing interaction strength. These predictions are borne out by the simulations. The modified Weiss model gives the best agreement with simulation, and its range of validity is limited to moderate, but realistic, values of the dipolar coupling constant.

Short-time dynamics and decay mechanism of E,E-2,4-hexadienal in the first light-absorbing S2(ππ*) state.

The initial nonadiabatic decay dynamics of E,E-2,4-hexadienal (HAL) in the light absorbing S2(ππ*) state were studied using resonance Raman spectroscopy and complete-active space self-consistent field (CASSCF) calculations. The UV and vibrational spectra were assigned on the basis of the UV absorption, Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-band resonance Raman spectra in cyclohexane and acetonitrile were obtained at 282.4, 273.9, 266.0, 252.7, and 245.9 nm excitation wavelengths, respectively, to probe the corresponding structural dynamics of HAL. The A-band absorption cross section and the corresponding absolute resonance Raman cross sections were simulated using a simple model based on the time-dependent wave-packet theory in a Brownian oscillator model. The geometric structures of the singlet electronic excited states and their curve-crossing points were optimized at the CASSCF level of theory. The obtained short-time structural dynamics in easy-to-visualize internal coordinates were then compared with the CASSCF-predicted structural-parameter changes of S2(ππ*)S1(nπ*)-n (n = 1-4). Our results indicate that the initial population of HAL in the S2 state ramifies in or nearby the Franck-Condon (FC) region, leading to five S2(ππ*) → S1(nπ*) internal conversion pathways due to the flexibility of the molecular chain and the different electronic resonant structures formed nearby FC of the S2 state. Then, the formed S1 transient species, which have different geometric structures and different energy partitions, undergo different photophysical processes, such as S1 → S0 internal conversion, S1 → T1 intersystem crossing, and the S1 → S'1 photoisomerization reaction. The substitution effect on the S2(ππ*) → S1(nπ*) internal conversion dynamics and the trans-cis photoisomerization reaction is proposed in terms of the p-π conjugation interaction or the p-σ superconjugation interaction.

Doublon dynamics of Bose-Fermi mixtures in optical lattices

We study the out-of-equilibrium dynamics of a dilute, lattice-confined Bose-Fermi mixture initialized in a highly excited state consisting of boson-fermion pairs (doublons) occupying single lattice sites. This system represents a paradigmatic case for studying relaxation dynamics in strongly correlated systems, and provides a versatile platform for studying thermalization and localization phenomena. We provide analytical expressions for the short-time decay of isolated doublons and small doublon clusters due to the competition between tunneling and interparticle interactions. We also discuss a mechanism for long-time decay that crucially depends on the quantum statistics of the particles constituting the doublon, namely, the conversion of pairs of neighboring doublons into an unpaired fermion and a site with a fermion and two bosons. Building on these insights, we develop a cluster expansion method to describe the dynamics in extended systems and compare it to numerically exact matrix product state simulations in one dimension. Finally, we discuss how our predictions can be observed in experiments with ultracold heteronuclear molecules.

Nonequilibrium Majorana dynamics by quenching a magnetic field in Kitaev spin liquids

The honeycomb Kitaev spin model provides a quantum spin liquid in the ground state, where the spin excitations are fractionalized into itinerant and localized Majorana fermions; the former spectrum has a broad continuum ranging up to a high energy, while the latter has a sharp peak at a low energy. Despite tremendous efforts, it remains elusive to clearly identify these distinct Majorana excitations in experiments. Here we show their manifestation in the time evolution after quenching the magnetic field, by using the time-dependent Majorana mean-field theory for both the ferromagnetic and antiferromagnetic Kitaev models. We find that the transient spin dynamics from the quantum spin liquid states is qualitatively different from the conventional spin precessions by the quench from the high-field forced-ferromagnetic state. We obtain peculiar time evolutions with distinct time scales, i.e., short-time decay of high-energy components associated with the itinerant Majorana excitations, and long-lived excitations at a low energy by the localized ones. These peculiar behaviors are caused by the energy transfer between the two Majorana quasiparticles after the field quench. Moreover, we find that the Majorana semimetal with the point nodes in equilibrium turns into a Majorana metal with the transient "Fermi surfaces" by the energy transfer. In particular, for the quench from the intermediate-field quantum spin liquid in the antiferromagnetic Kitaev model, the Fermi surfaces change their topology in the time evolution, which is regarded as a dynamical version of the Majorana "Lifshitz transition". Our results unveil that the real-time dynamics provides another route to not only the identification of the fractional Majorana excitations in candidate materials of Kitaev magnets but also unprecedented quantum phases that cannot be stabilized as the equilibrium states.

Quenched many-body quantum dynamics with k-body interactions using q-Hermite polynomials

In an m particle quantum system, the rank of interactions and the nature of particles (fermions or bosons) can strongly affect the dynamics of the system. To explore this, we study the nonequilibrium dynamics with particles in a one-body mean-field and quenched by an interaction of body-rank k = 2, 3, …, m. Using fermionic embedded Gaussian orthogonal ensembles (EGOEs) and bosonic embedded Gaussian orthogonal ensembles (BEGOEs) of one plus k-body interactions (also the unitary variants EGUE and BEGUE), it is seen that the short time decay of the survival probability of many-particle systems is given by the Fourier transform of the generating function of the q-Hermite polynomials. Deriving the formulas for q for both fermion and boson systems as a function of m, k and the number of single particle states N, we have verified that the Fourier transform of agrees very well with the numerical ensemble calculations for both fermion and boson systems. These results bridge the gap between the known results for k = 2 and k = m.

Inducing nontrivial qubit coherence through a controlled dispersive environment

We show how the dispersive regime of the Jaynes-Cummings model may serve as a valuable tool to the study of open quantum systems. We employ it in a bottom-up approach to build an environment that preserves qubit energy and induces varied coherence dynamics. We then present the derivation of a compact expression for the qubit coherence, applied here to the case of a finite number of thermally populated modes in the environment. We also discuss how the model parameters can be adjusted to facilitate the production of short-time monotonic decay (STMD) of the qubit coherence. Our results provide a broadly applicable platform for the investigation of energy-conserving open system dynamics which is fully within the grasp of current quantum technologies.

Local and global time decay for parabolic equations with super linear first-order terms

We study a class of parabolic equations having first order terms with superlinear (and subquadratic) growth. The model problem is the so-called viscous Hamilton-Jacobi equation with superlinear Hamiltonian. We address the problem of having unbounded initial data and we develop a local theory yielding well-posedness for initial data in the optimal Lebesgue space, depending on the superlinear growth. Then we prove regularizing effects, short and long time decay estimates of the solutions. Compared to previous works, the main novelty is that our results apply to nonlinear operators with just measurable and bounded coefficients, since we totally avoid the use of gradient estimates of higher order. By contrast we only rely on elementary arguments using equi-integrability, contraction principles and truncation methods for weak solutions.

Dynamics of vibrational frequency fluctuations in deuterated liquid ammonia: roles of fluctuating hydrogen bonds and free ND modes

We present an ab initio molecular dynamics study of the roles of fluctuating hydrogen bonds and free ND modes in the dynamics of ND stretch frequency fluctuations in deuterated liquid ammonia. We have also looked at some of the other dynamical quantities such as diffusion and orientational relaxation and also structural quantities such as pair correlations and hydrogen bonding properties which are relevant in the current context. The time correlation function of ND stretch frequencies is found to decay with primarily two time scales: A short-time decay with a time scale of less than 100 fs arising from intermolecular motion of intact hydrogen bonds and also from fast hydrogen bond breaking and a longer time scale of about 500 fs which can be assigned to the lifetime of free ND modes. Unlike water, in liquid ammonia an ND mode is found to remain free for a longer period than it stays hydrogen bonded and this longer lifetime of free ND modes determines the long-time behaviour of frequency fluctuations. Our hole dynamics calculations produced results of vibrational spectral diffusion that are similar to the decay of frequency time correlation. Inclusion of dispersion corrections is found to make the dynamics slightly faster.

Linearised dynamics and non-modal instability analysis of an impinging under-expanded supersonic jet

Non-modal instability analysis of the shear layer near the nozzle of a supersonic under-expanded impinging jet is studied. The shear layer instability is considered to be one of the main components of the feedback loop in supersonic jets. The feedback loop is observed in instantaneous visualisations of the density field where it is noted that acoustic waves scattered by the nozzle lip internalise as shear layer instabilities.A modal analysis describes the asymptotic limit of the instability disturbances and fails to capture short-time responses. Therefore, a non-modal analysis which allows the quantitative description of the short-time amplification or decay of a disturbance is performed by means of a local far-field pressure pulse. An impulse response analysis is performed which allows a wide range of frequencies to be excited. The temporal and spatial growths of the disturbances in the shear layer near the nozzle are studied by decomposing the response using dynamic mode decomposition and Hilbert transform analysis.The short-time response shows that disturbances with non-dimensionalised temporal frequencies in the range of 1 to 4 have positive growth rates in the shear layer. The Hilbert transform analysis shows that high non-dimensionalised temporal frequencies (>4) are dampened immediately, whereas low non-dimensionalised temporal frequencies (<1) are neutral. Both dynamic mode decomposition and Hilbert transform analysis show that spatial frequencies between 1 and 3 have positive spatial growth rates. Finally, the envelope of the streamwise velocity disturbances reveals the presence of a convective instability.

Full-dimensional treatment of short-time vibronic dynamics in a molecular high-order-harmonic-generation process in methane

We present derivation and implementation of the Multi-Configurational Strong-Field Approximation with Gaussian nuclear Wave Packets (MC-SFA-GWP) -- a version of the molecular strong-field approximation which treats all electronic and nuclear degrees of freedom, including their correlations, quantum-mechanically. The technique allows, for the first time, realistic simulation of high-harmonic emission in polyatomic molecules without invoking reduced-dimensionality models for the nuclear motion or the electronic structure. We use MC-SFA-GWP to model isotope effects in high-harmonics generation (HHG) spectroscopy of methane. The HHG emission in this molecule transiently involves strongly vibronically-coupled $^2F_2$ electronic state of the $\rm CH_4^+$ cation. We show that the isotopic HHG ratio in methane contains signatures of: a) field-free vibronic dynamics at the conical intersection (CI); b) resonant features in the recombination cross-sections; c) laser-driven bound-state dynamics; as well as d) the well-known short-time Gaussian decay of the emission. We assign the intrinsic vibronic feature (a) to a relatively long-lived ($\ge4$ fs) vibronic wave packet of the singly-excited $\nu_4$ ($t_2$) and $\nu_2$ ($e$) vibrational modes, strongly coupled to the components of the $^2F_2$ electronic state. We demonstrate that these physical effects differ in their dependence on the wavelength, intensity, and duration of the driving pulse, allowing them to be disentangled. We thus show that HHG spectroscopy provides a versatile tool for exploring both conical intersections and resonant features in photorecombination matrix elements in the regime not easily accessible with other techniques.

Short-time dynamics and decay mechanism of 2(1H)-pyridinone upon excitation to the light-absorbing S4(21𝝅𝝅*) state

The excited-state structural dynamics and the decay mechanism of 2(1H)-pyridinone (NHP) after excitation to the S4(21ππ*) light-absorbing state were studied using resonance Raman spectroscopy and complete-active space self-consistent field (CASSCF) calculations. The B-band absorption cross-section and the corresponding absolute resonance Raman cross-sections were simulated using a simple model based on time-dependent wave-packet theory. The geometric structures of the singlet electronic excited states and their curve-crossing points were optimized at the CASSCF level of theory. The obtained short-time structural dynamics in easy-to-visualize internal coordinates were then compared with the CASSCF-predicted structural-parameter changes of S4(21ππ*)/S3(21nπ*)-MIN, S4(21ππ*)/S1(11nπ*)-MIN, and S4(21ππ*)-MIN. Our results indicate that the initial population of NHP in the S4 state bifurcates in or near the Franck-Condon region, leading to two predominant (S4S3-MIN and S4S1-MIN) internal conversion pathways. The lowest-lying S2(11ππ*) excited state is finally formed via subsequent internal conversions S3(21nπ*)/S2(11ππ*)-MIN and S1(11nπ*)/S2(11ππ*)-MIN. The enol-keto tautomeric mechanism does not seem to play a role. The decay mechanism in the singlet realm is proposed.