Geometric bonding effects in the X2A1, A2∑+u, and B2IIg states of Li2F

Published ab-initio and pseudopotential calculations for the dialkali halide systems suggest that the preferred co-linear geometry is for the metal to approach the metal end of the alkali halide. Here, ab-initio calculations on the Li2F system reveal that the well depth on the halide side in this radical is much deeper and is a local saddle-point associated with the ionic non-linear global minima. Although many features of the pseudopotential surfaces are confirmed, significant differences are apparent including the existence of a linear excited state instead of a triangular one, a considerably deeper global minimum some 50% lower in energy and a close approach between the X2A1 and the states, with the minimum 87 kJ mol-1 below the ground state asymptote. All the results can be rationalised as the avoided crossings between a long range, covalent potential dominant within the LiLiF geometry and an ionic state that forms the global minimum. Calculations on the 3rd 2A' potential indicate that even for Li + LiF collisions at ultracold temperatures the collision dynamics could involve as many as three electronic states.

Quasi-classical model of non-destructive wavepacket manipulation by intense ultrashort nonresonant laser pulses

A quasi-classical model (QCM) of nuclear wavepacket generation, modification and imaging by three intense ultrafast near-infrared laser pulses has been developed. Intensities in excess of 10(13) W cm(-2) are studied, the laser radiation is non-resonant and pulse durations are in the few-cycle regime, hence significantly removed from the conditions typical of coherent control and femtochemistry. The 1s sigma ground state of the D-2 precursor is projected onto the available electronic states in D-2(+) (1s sigma(g) ground and 2p sigma(u) dissociative) and D+ + D+ (Coulomb explosion) by tunnel ionization by an ultrashort 'pump' pulse, and relative populations are found numerically. A generalized non-adiabatic treatment allows the dependence of the initial vibrational population distribution on laser intensity to be calculated. The wavepacket is approximated as a classical ensemble of particles moving on the 1s sigma(g) potential energy surface (PES), and hence follow trajectories of different amplitudes and frequencies depending on the initial vibrational state. The 'control' pulse introduces a time-dependent polarization of the molecular orbital, causing the PES to be modified according to the dynamic Stark effect and the transition dipole. The trajectories adjust in amplitude, frequency and phase-offset as work is done on or by the resulting force; comparing the perturbed and unperturbed trajectories allows the final vibrational state populations and phases to be determined. The action of the 'probe' pulse is represented by a discrete internuclear boundary, such that elements of the ensemble at a larger internuclear separation are assumed to be photodissociated. The vibrational populations predicted by the QCM are compared to recent quantum simulations (Niederhausen and Thumm 2008 Phys. Rev. A 77 013404), and a remarkable agreement has been found. The applicability of this model to femtosecond and attosecond time-scale experiments is discussed and the relation to established femtochemistry and coherent control techniques are explored.

Quantum superpositions of crystalline structures

A procedure is discussed for creating coherent superpositions of motional states of ion strings. The motional states are across the structural transition linear-zigzag, and their coherent superposition is achieved by means of spin-dependent forces, such that a coherent superposition of the electronic states of one ion evolves into an entangled state between the chain's internal and external degrees of freedom. It is shown that the creation of such an entangled state can be revealed by performing Ramsey interferometry with one ion of the chain.

Analog of Rabi oscillations in resonant electron-ion systems

Quantum coherence between electron and ion dynamics, observed in organic semiconductors by means of ultrafast spectroscopy, is the object of recent theoretical and computational studies. To simulate this kind of quantum coherent dynamics, we have introduced in a previous article [L. Stella, M. Meister, A. J. Fisher, and A. P. Horsfield, J. Chem. Phys. 127, 214104 (2007)] an improved computational scheme based on Correlated Electron-Ion Dynamics (CEID). In this article, we provide a generalization of that scheme to model several ionic degrees of freedom and many-body electronic states. To illustrate the capability of this extended CEID, we study a model system which displays the electron-ion analog of the Rabi oscillations. Finally, we discuss convergence and scaling properties of the extended CEID along with its applicability to more realistic problems. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3589165]

Rydberg structure associated with core-excited autoionizing states of the LiH radical

We have investigated inner-shell excitation of the LiH + molecular ion by electron impact within several different collision models to delineate Rydberg autoionizing resonance structure associated with the LiH + (1σ2σ 2 2 Σ + ) core-excited threshold. The minimal representation requires only the retention of the 1σ and 2σ molecular orbitals, in which the core-excited state involves the promotion of a single electron into the 2σ orbital. This model is extended to include two further representations, in which both the 3σ and 4σ orbitals obtained from a self-consistent field calculation improve target representation, correlation and support additional autoionization channels. This affects the autoionization widths and to a lesser degree the positions of the LiH (1σ2σ 2 n s, n p 1,3 Σ + ) resonance series. Comparing our work with calculations on the counterpart atomic Be system assists in the assignment of the core-excited molecular resonance states. The results from our investigation provide helpful insights into the study of inner-shell transitions produced by electron or photon impact in more complex diatomic molecules.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

Étude de dispositifs électroniques moléculaires à l'aide de modèles simples

Cette thèse en électronique moléculaire porte essentiellement sur le développement d’une méthode pour le calcul de la transmission de dispositifs électroniques moléculaires (DEMs), c’est-à-dire des molécules branchées à des contacts qui forment un dispositif électronique de taille moléculaire. D’une part, la méthode développée vise à apporter un point de vue différent de celui provenant des méthodes déjà existantes pour ce type de calculs. D’autre part, elle permet d’intégrer de manière rigoureuse des outils théoriques déjà développés dans le but d’augmenter la qualité des calculs. Les exemples simples présentés dans ce travail permettent de mettre en lumière certains phénomènes, tel que l’interférence destructive dans les dispositifs électroniques moléculaires. Les chapitres proviennent d’articles publiés dans la littérature. Au chapitre 2, nous étudions à l’aide d’un modèle fini avec la méthode de la théorie de la fonctionnelle de la densité de Kohn-Sham un point quantique moléculaire. De plus, nous calculons la conductance du point quantique moléculaire avec une implémentation de la formule de Landauer. Nous trouvons que la structure électronique et la conductance moléculaire dépendent fortement de la fonctionnelle d’échange et de corrélation employée. Au chapitre 3, nous discutons de l’effet de l’ajout d’une chaîne ramifiée à des molécules conductrices sur la probabilité de transmission de dispositifs électroniques moléculaires. Nous trouvons que des interférences destructives apparaissent aux valeurs propres de l’énergie des chaînes ramifiées isolées, si ces valeurs ne correspondent pas à des états localisés éloignés du conducteur moléculaire. Au chapitre 4, nous montrons que les dispositifs électroniques moléculaires contenant une molécule aromatique présentent généralement des courants circulaires qui sont associés aux phénomènes d’interférence destructive dans ces systèmes. Au chapitre 5, nous employons l’approche « source-sink potential » (SSP) pour étudier la transmission de dispositifs électroniques moléculaires. Au lieu de considérer les potentiels de sources et de drains exactement, nous utilisons la théorie des perturbations pour trouver une expression de la probabilité de transmission, T(E) = 1 − |r(E)|2, où r(E) est le coefficient de réflexion qui dépend de l’énergie. Cette expression dépend des propriétés de la molécule isolée, en effet nous montrons que c’est la densité orbitalaire sur les atomes de la molécule qui sont connectés aux contacts qui détermine principalement la transmission du dispositif à une énergie de l’électron incident donnée. Au chapitre 6, nous présentons une extension de l’approche SSP à un canal pour des dispositifs électroniques moléculaires à plusieurs canaux. La méthode à multiples canaux proposée repose sur une description des canaux propres des états conducteurs du dispositif électronique moléculaire (DEM) qui sont obtenus par un algorithme auto-cohérent. Finalement, nous utilisons le modèle développé afin d’étudier la transmission du 1-phényl-1,3-butadiène branché à deux rangées d’atomes couplées agissant comme contacts à gauche et à la droite.

Electronic structure calculations of small AI_n (n = 2 - 8) clusters

The electronic states of small AI_n (n = 2 - 8) clusters have been calculated with a relativistic ab-initio MOLCAO Dirac-Fock-Slater method using numerical atomic DFS wave-functions. The excitation energies were obtained from a ground state calculation of neutral clusters, and in addition from negative clusters charged by half an electron in order to account for part of the relaxation. These energies are compared with experimental photoelectron spectra.

Thermodynamic functions of element 105 in neutral and ionized states

The basic thermodynamic functions, the entropy, free energy, and enthalpy, for element 105 (hahnium) in electronic configurations d^3 s^2, d^3 sp, and d^4s^1 and for its +5 ionized state (5f^14) have been calculated as a function of temperature. The data are based on the results of the calculations of the corresponding electronic states of element 105 using the multiconfiguration Dirac-Fock method.

Fundamental interactions of molecules (Na_2, Na_3) with intense femtosecond laser pulses

The real-time dynamics of multiphoton ionization and fragmentation of molecules Na_2 and Na_3 has been studied in molecular beam experiments employing ion and electron spectroscopy together with femtosecond pump-probe techniques. Experiments with Na_2 and Na_3 reveal unexpected features of the dynamics of the absorption of several photons as seen in the one- and three-dimensional vibrational wave packet motion in different potential surfaces and in high laser fields: In Na_2 a second major resonance-enhanced multiphoton ionization (REMPI) process is observed, involving the excitation of two electrons and subsequent electronic autoionization. The possibility of controlling a reaction by controlling the duration of propagation of a wave packet on an electronically-excited surface is demonstrated. In high laser fields, the contributions from direct photoionization and from the second REMPI process to the total ion yield change, due to different populations in the electronic states participating in the multiphoton ionization (MPI) processes. In addition, a vibrational wave packet motion in the electronic ground state is induced through stimulated emission pumping by the pump laser. The 4^1 \summe^+_g shelf state of Na_2 is given as an example for performing frequency spectroscopy of highlying electronic states in the time domain. Pure wave packet effects, such as the spreading and the revival of a vibrational wave packet, are investigated. The three-dimensional wave packet motion in the Na_3 reflects the normal modes in the X and B states, and shows in addition the pseudorotational motion in the B state in real time.

High laser field effects in multiphoton ionization of Na_2

Femtosecond pump/probe multiphoton ionization experiments on Na_2 molecules are performed. The dependence of the total Na^+_2 ion signal on the delay time and the intensity of the femtosecond laser pulses is studied in detail. It is observed that molecular vibrational wavepacket motion in different electronic states dominates the time dependence of the ion signal. For higher laser intensities the relative contributions from the A ^1 \summe^+_u and the 2 ^1 \produkt__g states change dramatically, indicating the increasing importance of a two-electron versus a one-electron process. For even stronger fields (10 ^12 W/ cm²) a vibrational wavepacket in the electronic ground state X ^1 \summe^+_g is formed and its dynamics is also observed in the transient Na^+_2 signal. Time-dependent quantum calculations are presented. The theoretical results agree well with the experiment.

Analytical functions for the ground state potential surfaces of C3 (X 1 Σ g+) and HCN (X 1 Σ +)

Analytic functions have been obtained to represent the potential energy surfaces of C3 and HCN in their ground electronic states. These functions closely reproduce the available data on the energy, geometry, and force constants in all stable conformations, as well as data on the various dissociation products, and ab initio calculations of the energy at other conformations. The form of the resulting surfaces are portrayed in various ways and discussed briefly.

Theoretical calculation of absorption intensities of C2H and C2D

The theory of dipole-allowed absorption intensities in triatomic molecules is presented for systems with three close-lying electronic states of doublet multiplicity. Its derivation is within the framework of a recently developed variational method [CARTER, S., HANDY, N. C., PUZZARINI, C., TARRONI, R., and PALMIERI, P., 2000, Molec. Phys., 98,1967]. The method has been applied to the calculation of the infrared absorption spectrum of the C2H radical and its deuterated isotopomer for energies up to 10000 cm(-1) above the ground state, using highly accurate ab initio diabatic potential energy and dipole moment surfaces. The calculated spectra agree very well with those recorded experimentally in a neon matrix [FORNEY, D., JACOX, M. E., and THOMPSON, W. E., 1995, J. molee. Spectrosc., 170, 178] and assignments in the high energy region of the IR spectra are proposed for the first time.

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states (1(2)A', 2(2)A', 1(2)A '') of the C2Br radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, R-CC = 1.2621 angstrom, R-CBr = 1.7967 angstrom, < CCBr 156.1 degrees, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C2F and C2Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Sigma, Pi(1/2), Pi(3/2) vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5K have been calculated for the (CCBr)-C-12-C-12-Br-79 isotopomer, to an upper limit of 2000 cm(-1), using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.

Study of the spectroscopic properties and first hyperpolarizabilities of disperse azo dyes derived from 2-amino-5-nitrothiazole

The solvatochromism and other spectroscopic and photophysical characteristics of four azo disperse dyes, derived from 2-amino-5-nitrothiazole, were evaluated and interpreted with the aid of experimental data and quantum mechanical calculations. For the non-substituted compound two conformers, E and Z, were proposed for the isolated molecules, being the second one considerably less stable. The optimization of these structures in combination with a SCRF methodology (IEFPCM, Simulating the molecules in a continuum dielectric with characteristics of methanol), suggests that the Z form is not stable in solution. This same behaviour is expected for the substituted compounds, which is corroborated by experimental data presented in previous investigations [A.E.H. Machado, L.M. Rodrigues, S. Gupta, A.M.F. Oliveira-Campos, A.M.S. Silva, J. Mol. Struct. 738 (2005) 239-245]. For the substituted compounds, two forms derived from E conformer (A and R) are possible. Quantum mechanical data suggest for the isolated molecules, that the low energy absorption hand of the E conformers involve at least two close electronic states. having the low-lying excited state a (1)(n,pi*) nature, and being the S-2 state attributed to a (1)(pi,pi*) transition. The data also suggest a small energy gap between the absorption peaks of A and B, related to the easy conversion between these forms. For the structures optimized in combination with the applied SCRF methodology, an states inversion is observed for the Substituted compounds, with a considerable diminish of the energy gap between A and B absorption peaks. The electronic spectra of these compounds are quite sensitive to changes in the solvent polarity. The positive solvatochromism is more evident in aprotic solvents, probably due to the polarization induced by the solute. These compounds do not fluoresce at 298 K, but present a small but perceptible fluorescence at 77 K, which seems to be favoured by the nature of the group in the 2 `-position of the phenyl ring. Moreover, such compounds present expressive values for first hyperpolarizability, which implies in good non-linear optics (NLO) responses and photoswitching capability. (C) 2008 Elsevier B.V. All rights reserved.