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Polaritons - hybrid light-matter states formed in cavity - strongly change the properties of the underlying matter. In optical or plasmonic nanocavities, polaritons decay by radiative emission of the cavity, which is accessible experimentally. Due to the interaction of a molecule with the quantized radiation field, polaritons exhibit light-induced conical intersections (LICIs) which dramatically influence the nuclear dynamics of molecular polaritons. We show that ultrafast radiative emission from the lower polariton is controlled by the geometric phase imposed by the LICI. This finding provides insight into the process of emission and, furthermore, allows one to compute these signals by augmenting the Born-Oppenheimer approximation for polaritons with a geometric phase term.

After ionization of an inner-valence electron of molecules, the resulting cation-radicals store substantial internal energy which, if sufficient, can trigger ejection of an additional electron in an Auger decay usually followed by molecule fragmentation. In the environment, intermolecular Coulombic decay (ICD) and electron-transfer mediated decay (ETMD) are also operative, resulting in one or two electrons being ejected from a neighbor, thus preventing the fragmentation of the initially ionized molecule. These relaxation processes are investigated theoretically for prototypical heterocycle-water complexes of imidazole, pyrrole, and pyridine. It is found that the hydrogen-bonding site of the water molecule critically influences the nature and energetics of the electronic states involved, opening or closing certain relaxation processes of the inner-valence ionized system. Our results indicate that the relaxation mechanisms of biologically relevant systems with inner-valence vacancies on their carbon atoms can strongly depend on the presence of the electron-density donating or accepting neighbor, either water or another biomolecule.

By employing accurate state‐of‐the‐art many‐electron quantum‐chemistry methods, we establish that monocyclic carbon rings can accommodate Li guest atoms. The low‐lying electronic states of these endocircular systems are analyzed and found to include both charge‐separated states where the guest Li atom appears as a cation and the ring as an anion and encircled‐electron states where Li and the ring are neutral. The electron binding energies of the encircled‐electron states increase drastically at their highly symmetric equilibrium geometries with increasing size of the ring, and in Li@C24, this state becomes the ground state. Li is very weakly bound vertical to the rings in the low‐lying encircled‐electron states, hinting to van‐der‐Waals binding. Applcations are mentioned., Endocircular Li carbon rings exhibit two types of electronic states of very different nature, the ordering of which changes with the ring size. This enables possible interesting applications by excitations from the electronic ground states to states of different nature depending on the ring size.

The low-lying electronic states of neutral X@C60 (X = Li, Na, K, Rb) have been computed and analyzed by employing state-of-the-art high level many-electron methods. Apart from the common charge-separated states, well known to be present in endohedral fullerenes, one non-charge-separated state has been found in each of the investigated systems. In Li@C60 and Na@C60, the non-charge-separated state is a caged-electron state already discussed before for Li@C60. This indicates that the application of this low-lying state of Li@C60 discussed before is also applicable for Na@C60. In K@C60 and Rb@C60, the electronic radial distribution analysis shows that this hitherto unknown non-charge-separated state possesses a different nature from that of a caged-electron state.

We computed fully quantum nuclear dynamics, which accompanies electron transfer mediated decay (ETMD) in weakly bound polyatomic clusters. We considered two HeLi2 clusters – with Li2 being either in the singlet electronic ground state or in the triplet first excited state – in which ETMD takes place after ionization of He. The electron transfer from Li2 to He+ leads to the emission of another electron from Li2 into the continuum. Due to the weak binding of He to Li2 in the initial states of both clusters, the involved nuclear wavepackets are very extended. This makes both the calculation of their evolution and the interpretation of the results difficult. We showed that despite the highly delocalized nature of the wavepackets the nuclear dynamics in the decaying state is imprinted on the ETMD electron spectra. The analysis of the latter helps understanding the effect which electronic structure and binding strength in the cluster produce on the quantum motion of the nuclei in the decaying state. The results produce a detailed picture of this important charge transfer process in polyatomic systems., We computed fully quantum nuclear dynamics, which accompanies electron transfer mediated decay (ETMD) in weakly bound polyatomic clusters.

The endocircular Li@C

The coupling of a molecule and a cavity induces nonadiabaticity in the molecule which makes the description of its dynamics complicated. For polyatomic molecules, reduced-dimensional models and the use of the Born–Oppenheimer approximation (BOA) may remedy the situation. It is demonstrated that contrary to expectation, BOA may even fail in a one-dimensional model and is generally expected to fail in two- or more-dimensional models due to the appearance of conical intersections induced by the cavity., The coupling of a molecule and a cavity induces nonadiabaticity in the molecule which makes the description of its dynamics complicated.

Core-excited and core-ionized states created by absorption of X-ray photons carry an enormous energy of hundreds to thousands electronvolts. In the gas phase this energy is dissipated primarily in the Auger decay process or Auger decay cascades, whereby one or several electrons are emitted into the continuum producing multiply charged ions. Two interatomic electronic decay processes, interatomic Coulombic decay (ICD) and electron-transfer mediated decay (ETMD), ensure the efficient dissipation of energy beyond the Auger decay should X-ray absorption take place in a chemical medium characterized by weak van der Waals or hydrogen bonds. Numerous experiments and theoretical results have demonstrated that the Auger–interatomic decay cascades represent a common de-excitation mechanism of core vacancies in medium, whose length and complexity increase with increasing photon energy. Such cascades offer a means for very fast dissipation of the energy which is deposited by the photon into the system. They are also responsible for massive radiation damage to the molecules around the photoabsorption site. Surprisingly, ICD cascades remain a potent mechanism of energy dissipation also when the energy is invested in a cluster by a laser not as a single high energy photon but as multiple low energy ones. The recent research of the electronic decay in chemical media presented in this chapter strives to clarify the physical and chemical consequences of weakly subjecting bound clusters to the highly energetic light provided by modern light sources.

Interatomic Coulombic electron capture (ICEC) is an environment-assisted process in which a free electron can efficiently attach to a quantum system by transferring the excess energy of the electron capture to a neighbor ionizing it. Using the ab initio R-matrix method, we show that Fano profiles, resulting from interferences between the ICEC final states and resonant states, appear in the ICEC cross sections even at extremely large system-neighbor separations. We identify several types of resonant states depending on their decay pathways which may involve long-range electron and energy transfer. ICEC is a fundamental process and the interferences lead to substantial enhancement or decrease of the cross sections. The present investigation is therefore of general relevance in many contexts wherever electron capture in an environment takes place.

It is shown that a molecule can dissociate by the energy transferred from a remote neighbor. This neighbor can be an excited neutral or ionic atom or molecule. If it is an atom, then the transferred energy is, of course, electronic, and in the case of molecules, it can also be vibrational. Explicit examples are given which demonstrate that the transfer can be highly efficient at distances where there is no bonding between the transmitter and the dissociating molecule.

Determining the geometry of carbon rings is an ongoing challenge. Based on our calculations at a state-of-the-art level, we found that the C

International audience; Nonadiabaticity, i.e., the effect of mixing electronic states by nuclear motion, is a central phenomenon in molecular science. The strongest nonadiabatic effects arise due to the presence of conical intersections of electronic energy surfaces. These intersections are abundant in polyatomic molecules. Laser light can induce in a controlled manner new conical intersections, called light-induced conical intersections, which lead to strong nonadiabatic effects similar to those of the natural conical intersections. These effects are, however, controllable and may even compete with those of the natural intersections. In this work we show that the standard low-energy vibrational spectrum of the electronic ground state can change dramatically by inducing nonadiabaticity via a light-induced conical intersection. This generic effect is demonstrated for an explicit example by full-dimensional high-level quantum calculations using a pump-probe scheme with a moderate-intensity pump laser and a weak probe laser.

LiHe is an intriguing open-shell dimer. It is an extremely weakly bound system, and its vibrational bound-state radius extends far into the classically forbidden regions. Exciting helium into 1s2p leads to a

The current understanding of photoenzyme-catalyzed [2 + 2] cycloreversion repair of cyclobutane pyrimidine dimer (CPD) is that a photogenerated electron from the photolyase enzyme catalyzes the repair. This one-electron catalyzed repair is a sequential two-bond breaking cycloreversion of the cyclobutane center and involves a negative ion radical as an intermediate. Here, by resonantly capturing two exogenous low-energy electrons into the molecular field of a CPD, we show that the concerted synchronous two-bond breaking reaction, which is intermediate-free, and hence a safe repair, is feasible through two-electron catalysis.

New questions in fundamental physics and in other fields, which cannot be formulated adequately using traditional integral and differential calculus emerged recently. Fractional calculus was shown to describe phenomena where conventional approaches have been unsatisfactory. The driven damped fractional oscillator entails a rich set of important features, including loss of energy to the environment and resonances. In this paper, this oscillator with Caputo fractional derivatives is solved analytically in closed form. The exact solution is expressed in terms of generalized Mittag-Leffler functions. The standard driven-damped Harmonic Oscillator is recovered as a special case of non-fractional derivatives. In contradistinction to the standard oscillator, the solution of the fractional oscillator is shown to decay algebraically and to possess a finite number of zeros. Several decay patterns are uncovered and are a direct consequence of the asymptotic properties of the generalized Mittag-Leffler functions. Other interesting properties of the fractional oscillator like the momentum–position phase-plane diagrams and the time dependence of the energy terms are discussed as well.

Photoionization of the hydrogen atom by intense and short coherent laser pulses is investigated from first principles by a numerical solution of the time-dependent Schrodinger equation in the dipole-velocity gauge. The considered photon energies are resonant to the 1 s → 2 p excitation, and the pulse intensities are high enough to induce Rabi floppings. The computed resonance-enhanced two-photon ionization spectra as well as the three-photon above threshold ionization spectra exhibit pronounced multiple-peak patterns due to dynamic interference. Fingerprints of dynamic interference can also be seen directly in the radial density of the photoelectron. The impact of the variation of the pulse intensity and photon energy on the dynamic interference is investigated, and the angular distribution of the emitted electrons is analyzed in some details. The present precise numerical results confirm our previous theoretical predictions on the two-photon ionization spectra (Demekhin and Cederbaum, 2012) made within a minimal few-level model.

We report on high-level coupled-cluster calculations for the anion states of the smallest fullerene C20. Using the state-of-the-art EA-EOM-CCSD method we revealed that the C20- anion has five bound electronic states at the C20 neutral ground-state D3d equilibrium configuration. These are two pairs of 2Eu and 2A2u states and one 2A1g state. The binding energies vary from 2.05 eV for the most bound 2Eu state to

Nonadiabatic effects arise due to avoided crossings or conical intersections that are either present naturally in field-free space or induced by a classical laser field in a molecule. Recently, it was demonstrated that nonadiabatic effects in diatomics can also be created in an optical cavity. Here, the quantized radiation field mixes the nuclear and electronic degrees of freedom. We show the equivalence of using the cavity's quantized field and the classical laser field as usually done for molecules. This is demonstrated for NaI, which exhibits a pronounced natural (intrinsic) avoided crossing that competes with the avoided crossing induced by the field. Furthermore, rotating molecules exhibit light-induced conical intersections (LICIs) in classical laser light, and we also investigate the impact of these intersections. For NaI, we undoubtedly demonstrate a significant difference between the impact of the laser-induced avoided crossing and that of the LICI on the dynamics of the molecule.

We report on the experimental observation of the direct decay of a core vacancy in van der Waals clusters by emission of a fast electron from a neighboring atom. The process can be regarded as an interatomic Coulombic decay of core holes (core-level ICD). We identify it unambiguously by electron-electron and electron-electron-photon coincidence spectroscopy of the decay of 2p vacancies in Ar clusters. While several earlier works reported the absence of this channel, we find core-level ICD to be of considerable significance and quantify the branching ratio of this nonlocal electron emission to conventional local Auger decay as (0.8±0.2)%. Our results are supported by calculations on smaller clusters and show a reasonable agreement. This report on a successfully performed electron-electron-photon coincidence experiment provides a perspective for explorations of matter exposed to ionizing radiation. The observed core-level ICD is proposed to be of general importance for studies on charge redistribution after core-level photoionization where van der Waals clusters are often used as prototype systems.

LiHe is an extreme open-shell system. It is among the weakest bound systems known, and its mean interatomic distance extends dramatically into the classical forbidden region. Upon 1s → 2p excitation of He, interatomic Coulombic decay (ICD) takes place in which the electronically excited helium atom relaxes and transfers its excess energy to ionize the neighboring lithium atom. A substantial part of the decay is found to be to the dissociation continuum producing Li

Interatomic Coulombic decay (ICD) is a fundamental process between atoms or molecules via a neighbor interaction that produces a relaxation of an electronically excited atom or molecule when embedded in an environment. Due to the physical nature of the process, the electronic and nuclear degrees of freedom are coupled. In this paper, we study the ICD process for a lithium dimer by means of the electron and nuclear dynamics (END) approach. The END approach incorporates a full time-dependent description of the electronic and nuclear degrees of freedom, although its current version does not properly account for continuum states and has limitations in the electronic description by using a single determinantal wave function. Despite this, we confirm that the ICD process takes place via a dipole interaction that induces the nuclear motion of the dimer with a consequent electronic population transfer to higher excited states simulating the ionization process. When the dimer approaches a distance of around 11.5 a.u. (6 \AA{}), this ionization process takes place due to the dipole coupling and occurs at the place of the strongest attractive dipole force. Passing that point, we find that the two lithium atoms repel each other via a Coulomb explosion process followed with a consequent kinetic-energy release (KER). We determine the KER and the timing of the ICD process. We point out the strengths and weaknesses of the END approach and the required enhancements to account for a better description of the ICD process in a coupled electron and nuclear dynamics.

Interatomic-Coulombic-Decay (ICD) processes play an important role in the interaction of X-rays with biological systems. Here, we present the first successful experimental demonstration that enables and precisely times the outcome of an ICD process in an argon dimer, utilizing ultrafast XUV and IR radiation.

By employing large-scale high-level EA-EOM-CCSD calculations, we have computed and analyzed the low-lying states of neutral Li@C60. Apart from one state, all states are found to be charge-separated states of the type Li+@C60-. The new state is the first reported non-charge-separated state in endohedral alkali fullerenes. This caged-electron state is analyzed in detail. Arguments are given that in larger highly symmetric endohedral fullerenes the caged-electron state can be the electronic ground state of the system. HF and DFT calculations on Li@C180 indeed find that the caged-electron state is the ground state and that in its equilibrium geometry Li sits at the center of the cage. Applications are mentioned.

Charge transfer (CT) at avoided crossings of excited ionized states of argon dimers is observed using a two-color pump-probe experiment at the free-electron laser in Hamburg (FLASH). The process is initiated by the absorption of three 27-eV-photons from the pump pulse, which leads to the population of Ar2+*–Ar states. Due to nonadiabatic coupling between these one-site doubly ionized states and two-site doubly ionized states of the type Ar+*–Ar+, CT can take place leading to the population of the latter states. The onset of this process is probed by a delayed infrared (800 nm) laser pulse. The latter ionizes the dimers populating repulsive Ar2+ –Ar+ states, which then undergo a Coulomb explosion. From the delay-dependent yields of the obtained Ar2+ and Ar+ ions, the lifetime of the charge-transfer process is extracted. The obtained experimental value of (531 ± 136) fs agrees well with the theoretical value computed from Landau-Zener probabilities.

The increasing availability of X-ray free-electron lasers (XFELs) has catalyzed the development of single-object structural determination and of structural dynamics tracking in real-time. Disentangling the molecular-level reactions triggered by the interaction with an XFEL pulse is a fundamental step towards developing such applications. Here we report real-time observations of XFEL-induced electronic decay via short-lived transient electronic states in the diiodomethane molecule, using a femtosecond near-infrared probe laser. We determine the lifetimes of the transient states populated during the XFEL-induced Auger cascades and find that multiply charged iodine ions are issued from short-lived (∼20 fs) transient states, whereas the singly charged ones originate from significantly longer-lived states (∼100 fs). We identify the mechanisms behind these different time scales: contrary to the short-lived transient states which relax by molecular Auger decay, the long-lived ones decay by an interatomic Coulombic decay between two iodine atoms, during the molecular fragmentation., X線照射で始まる超高速反応の観測に成功 --レントゲンによるX線の発見から120年で初--. 京都大学プレスリリース. 2019-05-28.

Electron transfer mediated decay (ETMD) is a process responsible for double ionization of dopants in He droplets. It is initiated by producing He

Nonadiabatic coupling is absent between the electronic ground X and first excited (singlet) A states of formaldehyde. As laser fields can induce conical intersections between these two electronic states, formaldehyde is particularly suitable for investigating light-induced nonadiabaticity in a polyatomic molecule. The present work reports on the spectrum induced by light-the so-called field-dressed spectrum-probed by a weak laser pulse. A full-dimensional ab initio approach in the framework of Floquet-state representation is applied. The low-energy spectrum, which without the dressing field would correspond to an infrared vibrational spectrum in the X-state, and the high-energy spectrum, which without the dressing field would correspond to the X → A spectrum, are computed and analyzed. The spectra are shown to be highly sensitive to the frequency of the dressing light allowing one to isolate different nonadiabatic phenomena.

Nonadiabatic effects play a very important role in controlling chemical dynamical processes. They are strongly related to avoided crossings (AC) or conical intersections (CIs) which can either be present naturally or induced by classical laser light in a molecular system. The latter are named as "light-induced avoided crossings" (LIACs) and "light-induced conical intersections" (LICIs). By performing one or two dimensional quantum dynamical calculations LIAC and LICI situations can easily be created even in diatomic molecules. Applying such calculations for the NaI molecule, which is a strongly coupled diatomic in field free case, significant differences between the impact of the LIAC and LICI on the ground state population dynamics were observed. Moreover, obtained results undoubtedly demonstrate that the effect of the LIAC and LICI on the dynamics strongly depends on the intensity and the frequency of the applied laser field as well as the permanent dipole moments of the molecule.

Formamide, a simple model bio-molecule (HCONH2), is irradiated with high intensity, ultrashort pulses from an x-ray free electron laser. Ionic fragments resulting from photoionization and subsequent decay processes are recorded, as well as the electronic signature of the different inner shell ionization events that can take place during the x-ray pulses. The formation of double-core-hole states, where a second inner shell electron is removed before the first core hole has been refilled is observed in the electron spectra, recorded at all three sites (C, N, O) of the molecule. The individual ionization potentials are compared with results of ab initio calculations at different level of theory. Based on our results, future opportunities for advanced studies of inner-shell-induced electronic and nuclear dynamics are explored.

Doubly-excited atoms are known to autoionize. It is shown that in the presence of a neighboring atom, there is competition between autoionization and ICD (Interatomic Coulombic Decay) where the doubly-excited atom partially relaxes and the neighbor ionizes. Through a Rydberg series of doubly-excited states, the autoionization rate decreases in contrast to the ICD rate and ICD becomes dominant. Depending on the nature of the neighbor and the number of neighbors, other interatomic processes become operative even after autoionization, all demonstrating that the physics of doubly-excited species is strongly enriched in the presence of neighbors. Explicit examples are discussed.

LiHe is an intriguing open-shell dimer. It is an extremely weakly bound system, and its vibrational bound-state radius extends far into the classically forbidden regions. Exciting helium into 1s2p leads to a 2Σ and a 2Π state, in which lithium is in its ground state. These states are located above the ionization threshold of the Li atom, which makes them metastable, i.e., resonance states. Under these conditions, energy transfer between the atoms over large distances is feasible within the framework of interatomic Coulombic decay (ICD). These states are investigated theoretically; herein, we present and analyze the complex potential energy curves of the 2Σ and 2Π states, where their imaginary parts describe the decay rate of these resonance states. We employ the resonance via Pade approach to calculate these potentials. Thereby, we use the equation-of-motion coupled-cluster method to compute stabilization graphs as input data for the analytical dilation (via Pade) into the complex energy plane. The procedure is suitable for studying Feshbach resonances and ICD states such as the LiHe 2Σ and 2Π states. The resulting ab initio complex potential energy curves will be used in future work to describe the dynamics of the process HeLi + hν → He*Li → HeLi+ + eICD, which is amenable to experiment.

Bose-Einstein condensates (BECs) offer a fruitful, often uncharted ground for exploring physics of many-particle systems. In the present year of the MCTDHB project at the HLRS, we maintained and extended our investigations of BECs and interacting bosonic systems using the MultiConfigurational Time-Dependent Hartree for Bosons (MCTDHB) method and running the MCTDHB and MCTDH-X software packages on the Cray XC40 system Hazel Hen. The results we disseminate within this report comprise: (i) Entropies and correlations of ultracold bosons in a lattice; (ii) Crystallization of bosons with dipole-dipole interactions and its detection in single-shot images; (iii) Management of correlations in ultracold gases; (iv) Pulverizing a BEC; (v) Dynamical pulsation of ultracold droplet crystals by laser light; (vi) Two-component bosons interacting with photons in a cavity; (vii) Quantum dynamics of a bosonic Josephson junction and the impact of the range of the interaction; (viii) Trapped bosons in the infinite-particle limit and their exact many-body wavefunction and properties; (ix) Angular-momentum conservation in a BEC and Gross-Pitaevskii versus many-body dynamics; (x) Variance of an anisotropic BEC; and (xi) excitation spectrum of a weakly-interacting rotating BEC showing enhanced many-body effects. These are all basic and appealing, sometimes unexpected many-body results put forward with the generous allocation of computer time by the HLRS to the MCTDHB project. Finally, expected future developments and research tasks are prescribed, too.

The excitation spectrum of a highly-condensed two-dimensional trapped Bose-Einstein condensate (BEC) is investigated within the rotating frame of reference. The rotation is used to transfer high-lying excited states to the low-energy spectrum of the BEC. We employ many-body linear-response theory and show that, once the rotation leads to a quantized vortex in the ground state, already the low-energy part of the excitation spectrum shows substantial many-body effects beyond the realm of mean-field theory. We demonstrate numerically that the many-body effects grow with the vorticity of the ground state, meaning that the rotation enhances them even for very weak repulsion. Furthermore, we explore the impact of the number of bosons $N$ in the condensate on a low-lying single-particle excitation, which is describable within mean-field theory. Our analysis shows deviations between the many-body and mean-field results which clearly persist when $N$ is increased up to the experimentally relevant regime, typically ranging from several thousand up to a million bosons in size. Implications are briefly discussed.

The formation of light-induced conical intersections (LICIs) between electronic states of diatomic molecules has been thoroughly investigated over the past decade. In the case of running laser waves, the rotational, vibrational, and electronic motions couple via the LICI giving rise to strong nonadiabatic phenomena. In contrast to natural conical intersections (CIs) which are given by nature and hard to manipulate, the characteristics of LICIs are easily modified by the parameters of the laser field. The internuclear position of the created LICI is determined by the laser energy, while the angular position is given by the orientation of the transition dipole moment (TDM) with respect to the molecular axis. In the present communication, using MgH+ as a showcase example, we exploit the strong impact of the orientation of the TDMs exerted on the light-induced nonadiabatic dynamics. Comparing the photodissociations induced by parallel or perpendicular transitions, a clear signature of the created LICIs is revealed in the angular distribution of the photofragments.

When exposing molecules to resonant laser light, a new feature emerges. This feature is a conical intersection induced by the light, which cannot be avoided even in the case of diatomic molecules. The angle θ between the laser polarization and the molecular axis becomes the missing dynamical variable that, together with the stretching coordinate, establish the space in which the induced conical intersection (called the “light-induced conical intersection”, LICI) can exist. In contrast to natural CIs, which are ubiquitous in polyatomic systems and hard to manipulate, the light-induced conical intersections can easily be steered. Their positions can be controlled by the laser frequency, while the laser intensity determines the strength of the nonadiabatic coupling. The presence of a LICI in a molecular system provides a source for numerous static and dynamic nonadiabatic phenomena. Among others the LICI has a strong impact on the spectroscopic and dynamical properties of diatomic molecules. Motivated by recent theoretical works, several subjects are reviewed and analyzed showing that the LICI in diatomics gives rise to a variety of nonadiabatic phenomena.

Although the biological hazard of alpha-particle radiation is well-recognized, the molecular mechanisms of biodamage are still far from being understood. Irreparable lesions in biomolecules may not only have mechanical origin but also appear due to various electronic and nuclear relaxation processes of ionized states produced by an alpha-particle impact. Two such processes were identified in the present study by considering an acetylene dimer, a biologically relevant system possessing an intermolecular hydrogen bond. The first process is the already well-established intermolecular Coulombic decay of inner-valence-ionized states. The other is a novel relaxation mechanism of dicationic states involving intermolecular proton transfer. Both processes are very fast and trigger Coulomb explosion of the dimer due to creation of charge-separated states. These processes are general and predicted to occur also in alpha-particle-irradiated nucleobase pairs in DNA molecules.