Radiationless Transitions Research Articles

Interfering resonance as an underlying mechanism in the adaptive feedback control of radiationless transitions: Retinal isomerization.

Control of molecular processes via adaptive feedback often yields highly structured laser pulses that have eluded physical explanation. By contrast, coherent control approaches propose physically transparent mechanisms but are not readily visible in experimental results. Here, an analysis of a condensed phase adaptive feedback control experiment on retinal isomerization shows that it manifests a quantum interference based coherent control mechanism: control via interfering resonances. The result promises deep insight into the physical basis for the adaptive feedback control of a broad class of bound state processes.

An explanation of the very low fluorescence and phosphorescence in pyridine: a CASSCF/CASMP2 study

ABSTRACTIn this work, we applied the multiconfigurational complete active space self-consistent field method and the multiconfigurational second-order perturbation theory CASMP2 to study the fundamental excited states of pyridine and its possible photophysical and photochemical transformations. Our calculations, which are in agreement with the experimental results corresponding to excitations around the 0–0 transition, showed that the very low experimentally observed fluorescence of pyridine is due to the presence of two almost isoenergetic crossings, one of triple character, S1/T1/S0 and the other of S1/S0 character. Both crossings are below the minimum of S1(nπ*) and have a common transition state (S1(TS)) with a very low energy barrier (1.85 kcal/mol or 0.08 eV at the CASMP2 level of theory) separating them. A third triple crossing of the type S1/T1/S0 lying lower with respect to the other two elucidates the observed T1→S0 radiationless transition. This explains not only pyridine's very low fluorescence and phosphorescence but also its almost negligible photochemistry, showing that photophysics is the prevalent process in this molecule.

Assessing Excited State Energy Gaps with Time-Dependent Density Functional Theory on Ru(II) Complexes.

A set of density functionals coming from different rungs on Jacob's ladder is employed to evaluate the electronic excited states of three Ru(II) complexes. While most studies on the performance of density functionals compare the vertical excitation energies, in this work we focus on the energy gaps between the electronic excited states, of the same and different multiplicity. Excited state energy gaps are important for example to determine radiationless transition probabilities. Besides energies, a functional should deliver the correct state character and state ordering. Therefore, wave function overlaps are introduced to systematically evaluate the effect of different functionals on the character of the excited states. As a reference, the energies and state characters from multistate second-order perturbation theory complete active space (MS-CASPT2) are used. In comparison to MS-CASPT2, it is found that while hybrid functionals provide better vertical excitation energies, pure functionals typically give more accurate excited state energy gaps. Pure functionals are also found to reproduce the state character and ordering in closer agreement to MS-CASPT2 than the hybrid functionals.

Evolution of Excited-State Dynamics in Periodic Au28, Au36, Au44, and Au52 Nanoclusters.

Understanding the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au28, Au36, Au44, and Au52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast Sn → S1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO-LUMO gap excitation lacks ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core-shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.

Variable-temperature absorption and emission properties of 1,2-diphenylacetylene and 1,4-diphenylbuta-1,3-diyne derivatives

Variable-temperature absorption and emission data over the range 80–300 K have been collected for 1,2-diphenylacetylene (DPA) and its derivatives, as well as 1,4-diphenylbuta-1,3-diyne (DPB) derivatives in 2-methyltetrahydrofuran (2-MeTHF). Moreover, the influence of temperature on fluorescence lifetime and quantum yield has also been investigated. A strong coupling between solvation dynamics and solute structure is observed in the low-temperature regime as well as at intermediate temperature where the structure of the compound is evolving in the course of excited-state relaxation. Moreover, the dependency of fluorescence quantum yield on temperature indicates that the energy of activation of radiationless transition for 1,2-diphenylacetylene and its derivatives is larger than the activation energy of viscous flow of 2-MeTHF, while for 1,4-diphenylbuta-1,3-diyne derivatives the opposite is observed. This finding implies that the conformational change of DPA and its derivatives in the excited state in 2-MeTHF shows an activation energy, contrary to DPB and its derivatives for which conformational changes are barrierless.

Geometric Phase Effects in Nonadiabatic Dynamics near Conical Intersections

Dynamical consideration that goes beyond the common Born-Oppenheimer approximation (BOA) becomes necessary when energy differences between electronic potential energy surfaces become small or vanish. One of the typical scenarios of the BOA breakdown in molecules beyond diatomics is a conical intersection (CI) of electronic potential energy surfaces. CIs provide an efficient mechanism for radiationless electronic transitions: acting as "funnels" for the nuclear wave function, they enable rapid conversion of the excessive electronic energy into the nuclear motion. In addition, CIs introduce nontrivial geometric phases (GPs) for both electronic and nuclear wave functions. These phases manifest themselves in change of the wave function signs if one considers an evolution of the system around the CI. This sign change is independent of the shape of the encircling contour and thus has a topological character. How these extra phases affect nonadiabatic dynamics is the main question that is addressed in this Account. We start by considering the simplest model providing the CI topology: two-dimensional two-state linear vibronic coupling model. Selecting this model instead of a real molecule has the advantage that various dynamical regimes can be easily modeled in the model by varying parameters, whereas any fixed molecule provides the system specific behavior that may not be very illustrative. After demonstrating when GP effects are important and how they modify the dynamics for two sets of initial conditions (starting from the ground and excited electronic states), we give examples of molecular systems where the described GP effects are crucial for adequate description of nonadiabatic dynamics. Interestingly, although the GP has a topological character, the extent to which accounting for GPs affect nuclear dynamics profoundly depends on topography of potential energy surfaces. Understanding an extent of changes introduced by the GP in chemical dynamics poses a problem of capturing GP effects by approximate methods of simulating nonadiabatic dynamics that can go beyond simple models. We assess the performance of both fully quantum (wave packet dynamics) and quantum-classical (surface-hopping, Ehrenfest, and quantum-classical Liouville equation) approaches in various cases where GP effects are important. It has been identified that the key to success in approximate methods is a method organization that prevents the quantum nuclear kinetic energy operator to act directly on adiabatic electronic wave functions.

Abnormal photothermal effect of laser radiation on highly defect oxide bronze nanoparticles under the sub-threshold excitation of absorption

The mechanism of abnormal photo-thermal effect of laser radiation on nanoparticles of oxide bronzes has been proposed in this paper. The basic features of the observed effect are: a) sub-threshold absorption of laser radiation by the excitation of donor-like levels formed in the energy gap due to superficial defects of the oxide bronze nano-crystals; b) an interband radiationless transition of energy of excitation on deep triplet levels and c) consequent recombination occurring at the plasmon absorption. K or Na atoms thermally intercalated to the octahedral crystal structure of TiO2 in the wave SHS combustion generate acceptor levels in the gap. The prepared oxide bronzes of the non-stoichiometric composition NaxTiO2 and KxTiO2 were examined by high resolution TEM, and then grinded in a planetary mill with powerful dispersion energy density up to 4000 J/g. This made it possible to obtain nanoparticles about 50 nm with high surface defect density (1017–1019 cm-2 at a depth of 10 nm). High photo-thermal effect of laser radiation on the defect nanocrystals observed after its impregnation into cartilaginous tissue exceeds 7 times in comparison with the intact ones.

Insights into the Photophysics and Supramolecular Organization of Congo Red in Solution and the Solid State.

Steady-state and time-resolved absorption and fluorescence measurements are reported for Congo Red (CR) in aqueous and dimethylsulfoxide (DMSO) solutions. The very low fluorescence quantum yield (≈10-4 ) for CR in dilute solutions together with the absence of a triplet state indicates that internal conversion is the dominant deactivation route with more than 99.99 % of the quanta loss (attributed to the energy gap law for radiationless transitions). Although no direct evidence for trans-cis photoisomerization was obtained from absorption or fluorescence data, the global analysis of fs-transient absorption data indicates the presence of a photoproduct with a lifetime of ≈170 ps that is suggested to be associated with such a process. Spectral data for more concentrated CR solutions indicate the presence of oblique or twisted J-type aggregates. These results are compared with spectra for CR in the solid state (sodium salt) and intercalated in a layered double hydroxide via a one-step co-precipitation route. Powder XRD and electronic spectral data for the nanohybrid indicate that the CR guest molecules are intercalated as a monolayer consisting of slipped cofacial J-type aggregates.

Intersystem Crossing in Diplatinum Complexes.

Intersystem crossing (ISC) in solid [(C4H9)4N]4[Pt2(μ-P2O5(BF2)2)4], abbreviated Pt(pop-BF2), is remarkably slow for a third-row transition metal complex, ranging from τISC ≈ 0.9 ns at 310 K to τISC ≈ 29 ns below 100 K. A classical model based on Boltzmann population of one temperature-independent and two thermally activated pathways was previously employed to account for the ISC rate behavior. An alternative we prefer is to treat Pt(pop-BF2) ISC quantum mechanically, using expressions for multiphonon radiationless transitions. Here we show that a two-channel model with physically plausible parameters can account for the observed ISC temperature dependence. In channel 1, 1A2u intersystem crosses directly into 3A2u using a high energy B-F or P-O vibration as accepting mode, resulting in a temperature-independent ISC rate. In channel 2, ISC occurs via a deactivating state of triplet character (which then rapidly decays to 3A2u), using Pt-Pt stretching (160 cm-1) as a distorting mode to provide the energy needed. Fitting indicates that the deactivating state, 3X, is moderately displaced (S = 0.5-3) and blue-shifted (ΔE = 1420-2550 cm-1) from 1A2u. Our model accounts for the experimental observation that ISC in both temperature independent and thermally activated channels is faster for Pt(pop) than for Pt(pop-BF2): in the temperature independent channel because O-H modes in the former more effectively accept than B-F modes in the latter, and in the thermally activated pathway because the energy gap to 3X is larger in the latter complex.

Full observation of ultrafast cascaded radiationless transitions from S2(ππ(∗)) state of pyrazine using vacuum ultraviolet photoelectron imaging.

A photoexcited molecule undergoes multiple deactivation and reaction processes simultaneously or sequentially, which have been observed by combinations of various experimental methods. However, a single experimental method that enables complete observation of the photo-induced dynamics would be of great assistance for such studies. Here we report a full observation of cascaded electronic dephasing from S2(ππ(*)) in pyrazine (C4N2H4) by time-resolved photoelectron imaging (TRPEI) using 9.3-eV vacuum ultraviolet pulses with a sub-20 fs time duration. While we previously demonstrated a real-time observation of the ultrafast S2(ππ(*)) → S1(nπ(*)) internal conversion in pyrazine using TRPEI with UV pulses, this study presents a complete observation of the dynamics including radiationless transitions from S1 to S0 (internal conversion) and T1(nπ(*)) (intersystem crossing). Also discussed are the role of (1)Au(nπ(*)) in the internal conversion and the configuration interaction of the S2(ππ(*)) electronic wave function.

Relativistic calculations of K-, L- and M-shell X-ray production cross-sections by electron impact for Ne, Ar, Kr, Xe, Rn and Uuo

In this work, we derive X-ray production cross-sections from electron-impact ionization cross-sections for Ne, Ar, Kr, Xe, Rn, and Uuo, calculated in the modified relativistic binary-encounter-Bethe model, and using as the only input parameter the binding energies obtained in the Dirac-Fock approach. Radiative and radiationless transition probabilities necessary to compute the inter- and intra-shell atomic yields were calculated in the same approach. Shell electron-impact ionization cross-sections and X-ray production cross-sections are compared with the corresponding cross-sections retrieved from the National Institute of Standards and Technology Reference Database and available experimental data.

Communication: GAIMS--Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes.

Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.

Calculations of photo-induced X-ray production cross-sections in the energy range 1–150 keV and average fluorescence yields for Zn, Cd and Hg

In this paper, we calculate the K-, L- and M-shells X-ray production, and X-ray fluorescence cross-sections after photo-induced ionization, for Zn, Cd, and Hg, and for incident photon energy range from 1 to 150 keV. For this purpose, the corresponding average fluorescence yields for Zn, Cd, and Hg as well as the photoionization cross-sections were calculated using the Dirac–Fock method. Subshell fluorescence, intrashell and intershell yields are obtained consistently from radiative and radiationless transitions calculated in the exact same method. A comprehensive account of the relations between the X-ray production, X-ray fluorescence cross-sections and the photoionization cross-sections and these yields is presented. Comparisons are made with results from other authors. The obtained values for the photoionization cross-sections are in good agreement with the widely used data of Scofield in the studied energy range. However our results for the X-ray fluorescence cross sections seem to favor some data relatively to others. The energy dependence of the average fluorescence yields is discussed, in particular, the reliability of extrapolated data for lighter elements from measurements and calculations in heavier elements above the inner shell absorption edges is questioned. Tabulated data on photoionization and X-ray production cross-sections are presented for the incident photon energy range 1–150 keV in steps of 1 keV.

PDT-correlated photophysical properties of thienopyrrole BODIPY derivatives. Theoretical insights

Absorption electronic spectra, singlet-triplet energy gaps and spin–orbit matrix elements of thienopyrrole BODIPY derivatives, recently synthesized and proposed as potential photosensitizers in photodynamic therapy (PDT), have been computed by means of density functional theory (DFT) and time-dependent DFT approaches. A benchmark on structural parameters and maximum absorption wavelengths of different exchange-correlation functionals in combination with two basis set has been performed. The singlet-triplet energy gaps found are consistent with their possible application in PDT. The investigated molecules possess two excited triplet states (T1 and T2) that lie below and approximately at the same energy of the excited singlet one (S1), respectively. Both the radiationless transitions between S1 and triplet states contribute to the intersystem spin crossing efficiency, which in turn increases the production of singlet oxygen. Comparing their properties with those of agents currently used in PDT, one of them could be potentially used as photosensitizer for singlet oxygen production.

Suppressing molecular motions for enhanced room-temperature phosphorescence of metal-free organic materials.

Metal-free organic phosphorescent materials are attractive alternatives to the predominantly used organometallic phosphors but are generally dimmer and are relatively rare, as, without heavy-metal atoms, spin–orbit coupling is less efficient and phosphorescence usually cannot compete with radiationless relaxation processes. Here we present a general design rule and a method to effectively reduce radiationless transitions and hence greatly enhance phosphorescence efficiency of metal-free organic materials in a variety of amorphous polymer matrices, based on the restriction of molecular motions in the proximity of embedded phosphors. Covalent cross-linking between phosphors and polymer matrices via Diels–Alder click chemistry is devised as a method. A sharp increase in phosphorescence quantum efficiency is observed in a variety of polymer matrices with this method, which is ca. two to five times higher than that of phosphor-doped polymer systems having no such covalent linkage.

Intramolecular radiationless transition or background cosmic field effect in NO2

Optical excitation induces a transition in NO2 from a ground state |a> to an excited state |b>. The state |b> is not stable. The molecule evolves irreversibly from |b> to a state |c> in a time τ0≈3μs. We investigate the transition from |b> to |c> by analysing results of molecular beam and static gas experiments, and we conclude that the irreversible evolution is either an intramolecular radiationless transition of a symmetric to an asymmetric configuration of the isolated NO2 or the effect of a background cosmic field inducing a parity nonconserving transition from |b> to |c>.

Quenching the scintillation in CF4 Cherenkov gas radiator

CF4 is used as a Cherenkov gas radiator in one of the Ring Imaging Cherenkov detectors at the LHCb experiment at the CERN Large Hadron Collider. CF4 is well known to have a high scintillation photon yield in the near and far VUV, UV and in the visible wavelength range. A large flux of scintillation photons in our photon detection acceptance between 200 and 800nm could compromise the particle identification efficiency. We will show that this scintillation photon emission system can be effectively quenched, consistent with radiationless transitions, with no significant impact on the photons resulting from Cherenkov radiation.

Ultrafast multi-level logic gates with spin-valley coupled polarization anisotropy in monolayer MoS2.

The inherent valley-contrasting optical selection rules for interband transitions at the K and K′ valleys in monolayer MoS2 have attracted extensive interest. Carriers in these two valleys can be selectively excited by circularly polarized optical fields. The comprehensive dynamics of spin valley coupled polarization and polarized exciton are completely resolved in this work. Here, we present a systematic study of the ultrafast dynamics of monolayer MoS2 including spin randomization, exciton dissociation, free carrier relaxation, and electron-hole recombination by helicity- and photon energy-resolved transient spectroscopy. The time constants for these processes are 60 fs, 1 ps, 25 ps, and ~300 ps, respectively. The ultrafast dynamics of spin polarization, valley population, and exciton dissociation provides the desired information about the mechanism of radiationless transitions in various applications of 2D transition metal dichalcogenides. For example, spin valley coupled polarization provides a promising way to build optically selective-driven ultrafast valleytronics at room temperature. Therefore, a full understanding of the ultrafast dynamics in MoS2 is expected to provide important fundamental and technological perspectives.

Effect of Atom Substitution in Chalcogenodiazole-Containing Thermally Activated Delayed Fluorescence Emitters on Radiationless Transition

Radiationless transition between the lowest singlet (S1) and triplet (T1) excited states in the thermally activated delayed fluorescence (TADF) were investigated with respect to molecular design. The photophysical, transient photoluminescence and electroluminescence (EL) characteristics of two chalcogenodiazole-containing TADF emitters were compared. These contained 1,3,4-oxadiazole or 1,3,4-thiadiazole. The effect of substituting oxygen with sulfur on TADF was caused by an electron-pair-accepting conjugative effect. This effect resulted from the vacant 3d-orbitals of divalent sulfur in the thiadiazole heteroring. Atom substitution narrowed the gap between the highest occupied and lowest unoccupied molecular orbital energy levels, and enhanced S1 → T1 intersystem crossing. These effects resulted from the enhanced acceptor strength and orbital angular momentum by the vacant 3d-orbitals of sulfur. Atom substitution increased the contribution of the delayed fluorescence component to the total EL efficiency (...

Quantum dynamics of radiationless electronic transitions including normal modes displacements and Duschinsky rotations: a second-order cumulant approach.

An analytical expression for the population dynamics of electronic radiationless transitions has been derived from the second order expansion of the quantum evolution operator in the Liouville space and the cumulant theory. The expression includes the effect of both normal mode displacements and Duschinsky rotations and allows to take into account both equilibrium and nonequilibrium initial conditions. The methodology has been applied to model the electron-transfer process between the accessory bacteriochlorophyll and the bacteriopheophytine in bacterial reactions centers, providing a rate in good agreement with experimental findings.