Real-time ab initio simulations of excited carrier dynamics in carbon nanotubes

Combining time-dependent density functional calculations for electrons with molecular dynamics simulations for ions, we investigate the dynamics of excited carriers in a (3,3) carbon nanotube at different temperatures. Following an hnu=6.8 eV photoexcitation, the carrier decay is initially dominated by efficient coupling to electronic degrees of freedom. At room temperature, the excitation gap is reduced to nearly half its initial value after approximately 230 fs, where coupling to ionic motion starts dominating the decay. We show that the onset point and damping rate in the phonon regime change with initial ion velocities, a manifestation of temperature-dependent coupling between electronic and ionic degrees of freedom.     

Bonded exciplex formation from stacked thymine and adenine: semiclassical simulations

The nonradiative decay of a π-stacked adenine and thymine, following excitation of thymine by an ultrafast laser pulse, was studied by semiclassical dynamics simulations. The simulation found that a bonded exciplex is formed after excitation due to strong interaction between the stacked bases. The strong interaction significantly lowers the energy gap between the LUMO and HOMO and consequently facilitates the deactivation of the electronically excited molecule. It also restricts the deformation vibration of the excited thymine molecule, which slows down the coupling between the HOMO and LUMO energy levels and delays the deactivation of the excited adenine molecule to the electronic ground state.     

Tautomer contributions to the near UV spectrum of guanine: towards a refined picture for the spectroscopy of purine molecules

By using depopulation laser techniques, like IR-UV population labeling coupled to mass-selected R2PI detection, we confirm that four tautomers are responsible for the near UV spectroscopy (310-280 nm) of guanine: two enol and two keto forms, each pair having a 7NH and a 9NH form. Besides the UV spectroscopy of each tautomer, additional information on the excited state nature and dynamics is obtained from fluorescence studies. In particular, the quenching of fluorescence beyond 285 nm, the existence of a background absorption, as well as the existence of a strongly red-shifted component in the fluorescence emission provides evidence for a strong electronic mixing in the excited state together with an efficient non-radiative process. The details of these features are found to be tautomer-dependent. Comparison of the present results with literature data on other purine molecules, like adenine or 9-substituted guanines, enables us to propose a new insight on the spectroscopy and dynamics of the purine molecules. First, a large variability of the tautomer distribution in the gas phase is found within the purine family, in particular a molecular change, as simple as a 9-methylation on guanine, can reduce the tautomer distribution to a single species (enol form). Since the absorption spectrum is tautomer-dependent as well as substituent-dependent, it turns out that the tautomer population is one of the major parameters that control the overall shape of the UV spectrum. Second, the excited state model, often evoked in the literature, which involves electronic coupling between excited states of different natures, namely ππ^* and nπ^* states, might account for the present fluorescence measurements on guanine, providing an extensive excited state electronic mixing is assumed for these systems. Received 24 June 2002 Published online 13 September 2002     

Enhanced dissociation of H2+ into highly excited states by UV pulses

We theoretically study the dissociation of H₂⁺ by UV laser pulses as a function of the photon energy ω of the pulse. Our results show that pronounced enhancements of the dissociation into highly excited electronic states can be achieved at some critical ω. This is found to be attributed to a consecutively resonant excitation mechanism where the population is first transferred to the first excited state by absorbing one photon and then to higher states by absorbing another one or more photons at the same internuclear distance. This study indicates that the strong coupling between the lowest two states of H₂⁺ can significantly affect the dissociation through higher lying states.     

Entangling quantum gate in trapped ions via Rydberg blockade

We present a theoretical analysis of the implementation of an entangling quantum gate between two trapped Ca⁺ ions which is based on the dipolar interaction among ionic Rydberg states. In trapped ions, the Rydberg excitation dynamics is usually strongly affected by mechanical forces due to the strong couplings between electronic and vibrational degrees of freedom in inhomogeneous electric fields. We demonstrate that this harmful effect can be overcome using dressed states that emerge from the microwave coupling of nearby Rydberg states. At the same time. these dressed states exhibit long-range dipolar interactions which we use to implement a controlled adiabatic phase gate. Our study highlights a route toward a trapped ion quantum processor in which quantum gates are realized independently of the vibrational modes.     

有机发光材料中的三重激发态

有机发光材料有望广泛应用于新一代柔性光电子器件。由于自旋多重性,有机分子发光材料 中单重激发态和三重激发态转换较慢,限制有机发光器件特别是电注入荧光器件的效率。我们介绍 下近年来通过分子设计操控激发不同时间尺度三重态的动力学来突破这一限制的策略,通过控制激 发单重态和激发三线态之间的电子耦合,利用热激子系间窜越、反向系间窜越、激发三重态稳定化 等过程能够有效提高有机发光材料的发光效率。在此基础上实现的热活化延迟荧光、有机长余辉发 光等在有机发光二极管、传感器、生物成像等领域有重要潜在应用价值。     

分子间相互作用对有机分子发光性质的影响

有机固态发光材料因其在显示器、激光和光通信等领域的应用前景而受到越来越多的关注. 与单分子相比,有机固态中存在各种弱分子间相互作用,这些相互作用有时会对激发态性质和能量耗散途径产生较大的影响,从而产生较强的荧光或磷光. 因此揭示有机固态发光的内在机制是非常必要的. 本综述通过总结从单分子到聚集态激发态的几何结构、电子结构、电子振动耦合和能量耗散动力学的变化,简要概括了分子间相互作用如何诱导有机固体产生强荧光、热激活延迟荧光和室温磷光. 本综述希望能帮助深入理解有机固体的激发态特性,从而为设计优秀的固态发光材料提供思路.     

Fast polariton relaxation in strongly coupled organic microcavities

We consider the regime of strong light-matter coupling in an organic microcavity, where large Rabi splitting can be achieved. As has been shown, the excitation spectrum of such a structure, besides coherent polaritonic states, contains a number of strongly spatially localized incoherent excited states. These states form the majority of the excited states of the microcavity and are supposed to play the decisive role in the relaxation dynamics of the excitations in the microcavity. We consider the non-radiative transition from an incoherent excited state into one of the coherent states of the lower polaritonic branch accompanied by emission of a high-energy intramolecular phonon. It is shown that this process may determine the lifetime of incoherent excited states in the microcavity. This observation may be important in the discussion of pump–probe experiments with short pulses. This process may also play an important role for the population of the lowest energy states in organic microcavities, and hence in the problem of condensation of cavity polaritons.     

Evidence for the purely electronic character of primary electron transfer in purple bacteria Rh. Sphaeroides

A quantum-chemical calculation of the excited electronic states of a Rh. Sphaeroides reaction centre was performed. We discovered a new excited electronic state which can participate in electron transfer (ET). The energy gradient calculations showed that photoexcitation activates only high-frequency vibrational modes. This contradicts the widely accepted picture of ET resulting from vibrational wave packet motion. An alternative model is suggested where ET has a purely dissipative character and occurs only due to pigment--protein interaction. With this model, we demonstrate that oscillations in the femtosecond spectra can be caused by the new electronic state and non-Markovian character of dissipative dynamics.     

A theoretical forecast of the hydrogen bond changes in the electronic excited state for BN and its derivatives

The relationship between electronic spectral shifts and hydrogen-bonding dynamics in electronically excited states of the hydrogen-bonded complex is put forward. Hydrogen bond strengthening will induce a redshift of the corresponding electronic spectra, while hydrogen bond weakening will cause a blueshift. Time-dependent density function theory (TDDFT) was used to study the excitation energies in both singlet and triplet electronically excited states of Benzonitrile (BN), 4-aminobenzonitrile (ABN), and 4-dimethylaminobenzonitrile (DMABN) in methanol solvents. Only the intermolecular hydrogen bond C≡N...H-O was involved in our system. A fairly accurate forecast of the hydrogen bond changes in lowlying electronically excited states were presented in light of a very thorough consideration of their related electronic spectra. The deduction we used to depict the trend of the hydrogen bond changes in excited states could help others understand hydrogen-bonding dynamics more effectively.     

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part III: Theoretical investigation of oxalyl fluoride

We present a theoretical investigation of oxalyl fluoride (COF)₂ in the ground and the four lowest excited (two singlet and two triplet) electronic states of the n,π∗-type mainly with the CASPT2(8-6)/cc-pVTZ method. Geometries, vibrational frequencies, potential energy functions of internal rotation, and adiabatic electronic transition energies were obtained. The conformer energy difference and the barrier to internal rotation in the ground electronic state were extrapolated to the complete basis set limit. The planar trans and cis conformations were the most stable configurations for all five electronic states under study. We found that the allowed electronic transition of the cis conformer has a transition energy that is significantly higher than that predicted in previous studies. For the excited states, the internal rotation was found to be accompanied by significant non-planar distortion of both carbonyl fragments, indicating strong coupling between these molecular motions.     

Breakup of H2 in singly ionizing collisions with fast protons: channel-selective low-energy electron spectra

Dissociative as well as nondissociative single ionization of H2 by 6 MeV proton impact has been studied in a kinematically complete experiment by measuring the momentum vectors of the electron and the H+ fragment or the H+2 target ion, respectively. For the two ionization pathways, the electron spectra reveal the role of autoionization of the doubly and singly excited states of H2. The latter explicitly involve the coupling between the electronic and the nuclear motion of the molecule. This is a clear manifestation of a breakdown of the Born-Oppenheimer approximation.     

Vibronic coupling and implications in the copper related 1.014 eV photoluminescence spectrum in silicon

The 1.014 eV photoluminescence spectrum observed in Cu diffused, quenched silicon crystals exhibits a characteristic strong phonon sideband structure. It is shown that the intensity decrease of the no-phonon transition from 4.2 to 40 K is not due to vibronic coupling but originates in the population of excited electronic states of the defect. The thermal luminescence data and published lifetime measurements can consistently be explained by the electronic level scheme which was recently proposed.     

Anharmonic <Emphasis Type="Italic">T</Emphasis> ⊗ ɛ Jahn-Teller coupling in LiCaAlF<Subscript>6</Subscript>: Cr<Superscript>3+</Superscript>

For an octahedral system, we analyzed the coupling between the triple degenerate electronic states of a transition metal ion and the double degenerate vibration of the ligands of the host matrix. The vibrations of the ligands of the lattice are described by new anharmonic coherent states of the Morse potential. For the linear coupling between electronic states and anharmonic vibrations, we built the matrix elements from the interaction Hamiltonian and corresponding energy levels.     

Excited-state forces within a first-principles Green's function formalism

We present a new first-principles formalism for calculating forces for optically excited electronic states using the interacting Green's function approach with the GW Bethe-Salpeter-equation method. This advance allows for efficient computation of gradients of the excited-state Born-Oppenheimer energy, allowing for the study of relaxation, molecular dynamics, and photoluminescence of excited states. The approach is tested on photoexcited carbon dioxide and ammonia molecules, and the calculations accurately describe the excitation energies and photoinduced structural deformations.     

Electron transfer dynamics in the excited state studied by stochastic-Liouville equation

Electron transfer dynamics in the excited state is theoretically investigated by means of the stoschastic-Liouville equation. We evaluate time dependence of the density matrix for the three electronic states, the ground state, locally excited state, and the charge transfer state by solving the equation numerically. We treat the optical transition and electronic interaction in the excited states quantum mechanically to investigate these effects on the reaction dynamics.     

抛物量子点中强耦合磁极化子的性质

采用Pekar类型的变分方法研究了抛物量子点中强耦合磁极化子的基态和激发态的性质。计算了基态和激发态磁极化子的束缚能以及磁极化子的共振频率。讨论了这些量对回旋频率和有效限制强度的依赖关系,以及磁极化子光学声子平均数的性质,结果表明:由于Zeeman劈裂,抛物量子点中磁极化子的回旋共振频率劈裂为两支。基态和激发态磁极化子的束缚能以及磁极化子的共振频率都随回旋频率的增加而增大,随量子点的有效束缚强度的增大而减小。     

Shape dependent electronic structure and exciton dynamics in small In(Ga)As quantum dots

We present a study of the primary optical transitions and recombination dynamics in InGaAs self-assembled quantum nanostructures with different shape. Starting from the same quantum dot seeding layer, and depending on the overgrowth conditions, these new nanostructures can be tailored in shape and are characterized by heights lower than 2 nm and base lengths around 100 nm. The geometrical shape strongly influences the electronic and optical properties of these nanostructuctures. We measure for them ground state optical transitions in the range 1.25–1.35 eV and varying energy splitting between their excited states. The temperature dependence of the exciton recombination dynamics is reported focusing on the intermediate temperature regime (before thermal escape begins to be important). In this range, an important increase of the effective photoluminescence decay time is observed and attributed to the state filling and exciton thermalization between excited and ground states. A rate equation model is also developed reproducing quite well the observed exciton dynamics.