Resonance-enhanced optical reorientation of molecules in liquids via intermolecular interaction

Enhanced optical reorientation of molecules in a pure liquid was observed when the optical field was in resonance with the molecular electronic transition. The enhancement comes from photoinduced change in intermolecular interaction. Experimental results agree well with the time-dependent theory based on a mean-field model of intermolecular interaction.     

Ultrafast X-ray experiments on structural changes in single crystals of polar molecules

Intramolecular charge transfer in aminobenzonitrile (DIABN) single crystals is studied by a combination of ultrafast techniques. The intramolecular dynamics is probed by time-resolved spectroscopy in the UV/Vis and mid-IR. The intermolecular structural response is investigated by transient X-ray scattering and transmission experiments. A theoretical analysis shows that diffuse scattering and dipole solvation determine the X-ray data. The observed dynamics results from charge transfer reaction leading to strong local changes of molecular dipole moments and related structural rearrangements in the crystal.     

O3与O3分子间相互作用的理论研究

采用从头算方法,在B3LYP水平下对O3分子单体及其二聚体进行了几何结构优化,得到四种O3分子二聚体的稳定构型,并经MP2法、均衡法(Massage)分别校正了电子相关和基组叠加误差(BSSE),通过对分子中原子间的最短距离,分子间质心距离与各构型相互作用能的关系进行了分析、比较,得到了最稳定的构型,其对应的O3分子二聚体相互作用能为:-8.788 kJ/mol.     

Appearance of intermolecular interaction in the vibrational spectra of polyatomic XY3 molecules

We present the Raman spectra of liquid and solid PBr₃, AsCl₃, AsBr₃, and BiCl₃ between 77 and 500°K. We conjecture that ethane-like dimers of these phosphorus and arsenic trihalides exist between some temperature and the melting point. On the basis of our experimental results we analyze the change in the intramolecular force field of these molecules induced by the phase transitions and temperature, whence we calculate the frequency of vibration of the molecules relative to each other in the dimers: 2PBr₃, 2AsCl₃, 2AsBr₃. The same approach also gives the frequencies of the librational and translational modes of bismuth trichloride at 77°K.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 42–49, April, 1977.     

Optical study of anthracene molecules doped in fluorene single crystals

Properties of two luminescence centers, which are observed in anthracene-doped fluorene crystal as concentration increases, have been investigated to clarify their origin. Excitation spectra and concentration dependence of absorption spectra were measured and two types of luminescence are attributed to anthracene molecule pair centers with weak and strong interaction. Dipole-dipole interactions between two anthracence molecules of various configurations are estimated and possible configuration for two types of luminescence is proposed.     

Electron spin polarization of doublet state species due to interaction with excited triplet states in single crystals

Doublet states species trapped in crystalline solids show transient spin polarized EPR spectra if the crystal is illuminated by visible or UV light. The spin polarization is accounted for by the interaction of the doublet species with photoexcited triplet states. The mechanism of the process producing the spin polarization is examined and some experimental examples are discussed. The analysis of the time evolution of the transient variation of the EPR signal allows the measurements of the spin lattice relaxation time and in some cases of the diffusion rate of mobile triplet excitations in the crystal lattice.     

苯与PtH分子间电子相互作用的理论研究

采用从头算法在B3LYP水平分别对苯和PtH分子单体及其分子复合物体系(苯-PtH)进行了几何结构优化和振动频率计算,得到了3种苯-PtH分子复合物构型,研究了苯与PtH分子间相互作用对Pt-H键振动频率的影响,并得出了苯与PtH分子之间的相互作用能.     

Ultrafast and nanosecond laser-induced desorption of positive ions from lithium fluoride single crystals

We compare desorption of positive ions from lithium fluoride single crystals following pulsed laser excitation using either femtosecond (180 fs, 265 nm) or nanosecond (3 ns, 266 nm) sources. Following optical excitation, desorbed ions are mass analyzed using standard time-of-flight techniques. Several important differences between nanosecond and femtosecond excitation are revealed. Femtosecond excitation produces higher kinetic energy Li⁺ than does nanosecond excitation (10 eV vs. 5 eV) while nanosecond excitation yields significant quantities of impurity ions Na⁺ and K⁺, in addition to efficient Li⁺ emission. The Li⁺ desorption threshold is similar for both laser sources. This similarity is a surprising result, as sub-bandgap nanosecond pulses are only likely to excite defect states efficiently (via linear excitation), while the ultrahigh peak-power femtosecond pulses could in principle induce multiphoton and avalanche excitation. Femtosecond excitation results in much less complicated time-of-flight spectra, as predominantly Li⁺ is detected with some H⁺ also observed. We have measured the Li⁺ yield as a function of time delay between two sub-threshold femtosecond laser pulses. We find that the majority of the Li⁺ yield decays rapidly, largely within the fs pulse duration. However, a weak but measurable decay component of approximately 2 ps is indicated.     

Laser cooling of molecules via single spontaneous emission

A general scheme for reducing the center-of-mass entropy is proposed. It is based on the repetition of a cycle, composed of three concepts: velocity selection, deceleration and irreversible accumulation. Well-known laser techniques are used to represent these concepts: Raman π-pulse for velocity selection, STIRAP for deceleration, and a single spontaneous emission for irreversible accumulation. No closed pumping cycle nor repeated spontaneous emissions are required, so the scheme is applicable to cool a molecular gas. The quantum dynamics are analytically modelled using the density matrix. It is shown that during the coherent processes the gas is translationally cooled. The internal states serve as an entropy sink, in addition to spontaneous emission. This scheme provides new possibilities to translationally laser-cool molecules for high precision molecular spectroscopy and interferometry. Received 25 June 2002 / Received in final form 28 September 2002 Published online 12 November 2002 RID="a" ID="a"e-mail: ooi@spock.physik.uni-konstanz.de RID="b" ID="b"e-mail: Peter.Marzlin@uni-konstanz.de RID="c" ID="c"e-mail: Juergen.Audretsch@uni-konstanz.de     

High-fidelity quantum memory realized via Wigner crystals of polar molecules

The collective excitations of spin states of an ensemble of polar molecules are studied as a candidate for high-fidelity quantum memory. To avoid the collisional properties of the molecules, they are arranged in dipolar crystals under one or two dimensional trapping conditions. We calculate the lifetime of the quantum memory by identifying the dominant decoherence mechanisms and estimating their effects on gate operations when a molecular ensemble qubit is transferred to a microwave cavity.     

Theoretical study of molecular ordering in liquid crystals with the help of intermolecular interaction energy calculations

A theoretical analysis has been carried out to determine the molecular alignment of some nematic liquid crystals like DPAB (4, 4'-di-n-propoxy-azoxybenzene), EPAB (ethyl para-azoxybenzoate) and PAA (para-azoxyanisole). CNDO/2 method has been employed to evaluate the net atomic charge and atomic dipole components at each atomic centre of the molecules. Configurational energy has been computed using a modified Rayleigh-Schrodinger perturbation method at an interval of 1 Å in translation and 10° in rotation between a pair of DPAB molecules. On the basis of stacking, in-plane and terminal interaction energy calculations, all possible geometrical arrangements between a molecular pair have been considered. A comparative picture of molecular parameters like total energy, binding energy, total dipole moment etc., has been obtained. An attempt has been made to explain the nematogenic behaviour of liquid crystal and thereby develop a molecular model for liquid crystallinity.     

Ultrafast relaxation in quasi-one-dimensional organic molecular crystals

We present a comprehensive study of ultrafast relaxation properties of optical excitations in thin films of quasi-1D stacked organic materials PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) and MePTCDI (N,N'-dimethylperylene-3,4,9,10-dicarboximide) over five decades of time. Pump-probe experiments reveal excitonic intraband relaxation time constants of 65 fs for MePTCDI and 100 fs for PTCDA. The initial time-resolved luminescence anisotropy is consistent with the exciton model of Davydov-split states. The subsequent decay of the anisotropy can be explained with a thermally activated exciton hopping process. A full understanding of the pump-probe experiments calls for an explanation beyond the models presently available.     

Ultrafast optical switching in three-dimensional photonic crystals

We present the first experimental investigation of ultrafast optical switching in a three-dimensional photonic crystal made of a Si-opal composite. Ultrafast (30 fs) changes in reflectivity around the photonic stop band up to 1% were measured for moderate pump power (70 microJ/cm(2)). Short-lived photoexcited carriers in silicon induce changes in the dielectric constant of Si and diminish the constructive interference inside the photonic crystal. The results are analyzed within a model based on a two-band mixing formalism.     

Ultrafast Coulomb explosion imaging of molecules

Multiple ionization of small molecules leads to multifragmentation called Coulomb explosion. The atomic positions prior to the fragmentation event are determined from the multicharged fragments trajectories. Following the pioneering contribution of Prof. N.B. Delone on atomic ionization using strong laser fields, intense femtosecond laser pulses in the 10¹⁵ W cm^?2 range permit an efficient removal of valence electrons. Pulse durations have to be reduced to a few cycles in order to avoid any significant molecular stretching during multiple ionization. Pumpprobe excitation schemes offer promising perspectives for straightforward ultrafast Coulomb explosion imaging of excited and ionized molecular species.     

Giant formation rates of ultracold molecules via Feshbach-optimized photoassociation

Ultracold molecules offer a broad variety of applications, ranging from metrology to quantum computing. However, forming "real" ultracold molecules, i.e., in deeply bound levels, is a very difficult proposition. Here, we show how photoassociation in the vicinity of a Feshbach resonance enhances molecular formation rates by several orders of magnitude. We illustrate this effect in heteronuclear systems, and find giant rate coefficients even in deeply bound levels. We also give a simple analytical expression for the photoassociation rate and discuss future applications of the Feshbach-optimized photoassociation technique.     

Surface modification of lithium deuteride single crystals in interaction with the atmosphere

Interactions between the surface of lithium deuteride and atmosphere at room temperature are studied by Rutherford backscattering spectroscopy and recoil nuclei.