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International audience; The photodetachment spectrum of the nitrate anion (NO − 3) is simulated from first principles using wavepacket quantum dynamics propagation and a newly developed accurate full-dimensional fully coupled five state diabatic potential model. This model utilizes the recently proposed complete nuclear permutation inversion invariant artificial neural network diabatization technique [D. M. G. Williams and W. Eisfeld, J. Phys. Chem. A 124, 7608 (2020)]. The quantum dynamics simulations are designed such that temperature effects and the impact of near threshold detachment are taken into account. Thus, the two available experiments at high temperature and at cryogenic temperature using the slow electron velocity-map imaging technique can be reproduced in very good agreement. These results clearly show the relevance of hot bands and vibronic coupling between theX 2 A ′ 2 ground state and theB 2 E ′ excited state of the neutral radical. This together with the recent experiment at low temperature gives further support for the proper assignment of the ν 3 fundamental, which has been debated for many years. An assignment of a not yet discussed hot band line is also proposed.

International audience; We present fully ab initio calculations of second-overtone rovibrational line shapes of carbon monoxide perturbed by argon. The quantum mechanical scattering problem between CO and Ar is solved numerically for two different ab initio interaction potentials. We use the generalized Hess method to determine spectroscopic cross sections which describe the effect of collisions on each spectral line. Using these cross sections, we determine the line-shape parameters that we use to generate the Hartmann-Tran and speed-dependent billiard ball profiles. We compare the generated line shapes with high-quality experimental line profiles of five lines measured at five pressures between 0.01 and 1 atm. A subpercent agreement over the entire pressure range is obtained. Calculations for the P(9) line are used to inspect the effects of the two interaction potentials. The discrepancies for both the considered interaction potentials and the experiment are explained within the described theoretical framework. The presented results are the most accurate collisional line-shape calculations for a system with collision dynamics representative of atmospherically relevant species.

International audience; We present a procedure for generating the parameters of the Hartmann-Tran profile (HTP) from purely first principles calculations. Starting from an absorber-perturber interaction potential, we calculate S-matrices describing the effect of collisions on the absorbing molecule. We then use the generalized Hess method to calculate speed-dependent pressure shift and broadening parameters, and the complex Dicke parameter, ν opt , which accounts for such effects as the Dicke effect and correlations between dephasing and velocity-changing collisions. Based on these ab initio results, we derive the Hartmann-Tran profile parameters and evaluate the validity of the quadratic approximation of speed dependence and the hard-collision model of velocity-changing collisions adopted in the Hartmann-Tran profile. We also discuss the interpretation and speed dependence of ν opt. Finally, we evaluate the approximation scheme for temperature dependence of HTP line-shape parameters adopted in the 2016 edition of the HITRAN database.

International audience; Near-infrared spectroscopy of the C2H2–Ar, Kr complexes was performed in the spectral region overlapping the ν3/ν2 + ν4 + ν5 Fermi-type resonance of C2H2. The experiment was conducted along the HElium NanoDroplet Isolation (HENDI) technique in order to study the coupling dynamics between a floppy molecular system (C2H2–Ar and C2H2–Kr) and a mesoscopic quantum liquid (the droplet). Calculations were performed using a spectral element based close-coupling program and state-of-the-art 2-dimensional potential energy surfaces to determine the bound states of the C2H2–Ar and C2H2–Kr complexes and simulate the observed spectra. This furnished a quantitative basis to unravel how the superfluid and non-superfluid components of the droplet affect the rotation and the deformation dynamics of the hosted complex.

International audience; A recently developed scheme to produce high-dimensional coupled diabatic potential energy surfaces (PESs) based on artificial neural networks (ANNs) [D. M. G. Williams and W. Eisfeld, J. Chem. Phys. 149, 204106 (2019)] is tested for its viability for quantum dynamics applications. The method, capable of reproducing high-quality ab initio data with excellent accuracy, utilizes simple coupling matrices to produce a basic low-order diabatic potential matrix as an underlying backbone for the model. This crude model is then refined by making its expansion coefficients geometry-dependent by the output neurons of the ANN. This structure, strongly guided by a straightforward physical picture behind nonadiabatic coupling, combines structural simplicity with high accuracy, reproducing ab initio data without introducing unphysical artifacts to the surface, even for systems with complicated electronic structure. The properties of diabatic potentials obtained by this method are tested thoroughly in the present study. Vibrational/vibronic eigenstates are computed on theX andà states of NO 3 , a notoriously difficult Jahn-Teller system featuring strong nonadiabatic couplings and complex spectra. The method is investigated in terms of how consistently it produces dynamics results for PESs of similar (fitting) quality and how the results depend on the ANN size and ANN topography. A central aspect of this work is to understand the convergence properties of the new method in order to evaluate its predictive power. A previously developed, high-quality model utilizing a purely (high-order) polynomial ansatz is used as a reference to showcase improvements of the overall quality which can be obtained by the new method.

International audience; E ⊗ e Jahn-Teller (JT) systems are considered the prototype of symmetry-induced conical intersections and of the corresponding geometric phase effect (GPE). For decades, this has been analyzed for the most common case originating from C 3v symmetry and these results usually were generalized. In the present work, a thorough analysis of the JT effect, vibronic coupling Hamiltonians, GPE, and the effect on spectro-scopic properties is carried out for general Cnv symmetric systems (and explicitly for n = 3-8). It turns out that the C 3v case is much less general than often assumed. The GPE due to the vibronic Hamiltonian depends on the leading coupling term of a diabatic representation of the problem, which is a result of the explicit n, α, and β values of a Cnv Eα ⊗ e β system. Furthermore, the general existence of n/m (m ∈ N depending on n, α, and β) equivalent minima on the lower adiabatic sheet of the potential energy surface (PES) leads to tunneling multiplets of n/m states (state components). These sets can be understood as local vibrations of the atoms around their equilibrium positions within each of the local PES wells symmetrized over all equivalent wells. The local vibrations can be classified as tangential or radial vibrations, and the quanta in the tangential mode together with the GPE determine the level ordering within each of the vibronic multiplets. Our theoretical predictions derived analytically are tested and supported by numerical model simulations for all possible Eα ⊗ e β cases for Cnv symmetric systems with n = 3-8. The present interpretation allows for a full understanding of the complex JT spectra of real systems, at least for low excitation energies. This also opens a spectroscopic way to show the existence or absence of GPEs. Published under license by AIP Publishing. https://doi.

A new full-dimensional (6D) diabatic potential energy surface (PES) model is presented representing the five lowest PESs corresponding to the X 2 A 2 ′ , A 2 E ″ , and B 2 E ′ electronic states of the nitrate radical (NO3). It is based on high-level ab initio calculations of roughly 90000 energy data over a wide range of nuclear configurations and represents the energies with a root mean-squares (rms) error of about 100 cm−1. An accurate dipole surface was developed for the X state as well. The new PES model is used to re-investigate the infra-red (IR) spectrum corresponding to the electronic ground state by full dimensional quantum dynamics simulations. Vibrational eigenstates, IR transition probabilities, and isotopic shifts are computed and analyzed. Levels up to 2000 cm−1 are obtained and show good to excellent agreement with known experimental values. Some larger deviations are observed and discussed as well. The new results are in agreement with previous theoretical studies that the disputed ν 3 fundamental corresponds to a frequency of roughly 1022 cm−1 and that the prominent experimental feature observed at 1492 cm−1 is due to the 3 1 4 1 ( e ′ ) combination mode. Observed discrepancies in the IR intensities may be explained by coupling to the B state which is also analysed by diabatic decomposition of the eigenstates.

We apply the spectral element method to the determination of scattering and bound states of the multichannel Schr\"odinger equation. In our approach the reaction coordinate is discretized on a grid of points whereas the internal coordinates are described by either purely diabatic or locally diabatic (diabatic-by-sector) bases. Bound levels and scattering matrix elements are determined with spectral accuracy using relatively small numbers of points. The scattering problem is cast as a linear system solved using state-of-the-art sparse matrix non iterative packages. Boundary conditions can be imposed so to compute a single column of the matrix solution. A comparison with log-derivative propagators customarily used in molecular physics is performed. The same discretization scheme can also be applied to bound levels that are computed using direct scalable sparse-matrix solvers., Comment: 24 pages, 5 figures

The E-2 '' state of NO3, a prototype for the Jahn-Teller effect, has been an enigma and a challenge for a long time for both experiment and theory. We present a detailed theoretical study of the vibronic quantum dynamics in this electronic state, uncovering the effects of tunnelling, geometric phase, and symmetry. To this end, 45 vibronic levels of NO3 in the E-2 '' state are determined accurately and analyzed thoroughly. The computation is based on a high quality diabatic potential representation of the two-sheeted surface of the E-2 '' state developed by us [W. Eisfeld et al., J. Chem. Phys. 140, 224109 (2014)] and on the multi-configuration time dependent Hartree approach. The vibrational eigenstates of the NO3- anion are determined and analyzed as well to gain a deeper understanding of the symmetry properties of such D-3h symmetric systems. To this end, 61 eigenstates of the NO3- anion ground state are computed using the single sheeted potential surface of the (1)A(1) state published in the same reference quoted above. The assignments of both the vibrational and vibronic levels are discussed. A simple model is proposed to rationalize the computed NO3 spectrum strongly influenced by the Jahn-Teller couplings, the associated geometric phase effect, and the tunnelling. Comparison with the available spectroscopic data is also presented. Published by AIP Publishing.

International audience; We present quantum scattering calculations of 4 He and 3 He colliding with 87 Rb 2. For both helium isotopes, the elastic and inelastic rate coefficients are strongly influenced by the J = 1 partial wave. For the lighter isotope a strong resonance feature of the J = 1 partial wave is responsible for an extremely efficient vibrational relaxation process. We also perform bound-state calculations of the Rb 2 He complex for even Rb permutation symmetry and non-zero total angular momentum. The global Rb 2 He 3 Σ + u potential energy surface used supports four bound states for 4 He and a single one for 3 He. We propose an analysis of the 87 Rb 2 4 He spectrum separating the contributions of Rb 2 rotation and helium motion.

International audience; A scheme to produce accurate full-dimensional coupled diabatic potential energy surfaces including dissociative regions and suitable for dynamical calculations is proposed. The scheme is successfully applied to model the two-sheeted surface of the 2E″ state of the NO3 radical. An accurate potential energy surface for the NO−3NO3− anion ground state is developed as well. Both surfaces are based on high-level ab initio calculations. The model consists of a diabatic potential matrix, which is expanded to higher order in terms of symmetry polynomials of symmetry coordinates. The choice of coordinates is key for the accuracy of the obtained potential energy surfaces and is discussed in detail. A second central aspect is the generation of reference data to fit the expansion coefficients of the model for which a stochastic approach is proposed. A third ingredient is a new and simple scheme to handle problematic regions of the potential energy surfaces, resulting from the massive undersampling by the reference data unavoidable for high-dimensional problems. The final analytical diabatic surfaces are used to compute the lowest vibrational levels of NO−3NO3− and the photo-electron detachment spectrum of NO−3NO3− leading to the neutral radical in the 2E″ state by full dimensional multi-surface wave-packet propagation for NO3 performed using the Multi-Configuration Time Dependent Hartree method. The achieved agreement of the simulations with available experimental data demonstrates the power of the proposed scheme and the high quality of the obtained potential energy surfaces.

International audience; Following our work on the study of helium droplets and film doped with one electronically excited rubidium atom Rb(∗) ((2)P) [M. Leino, A. Viel, and R. E. Zillich, J. Chem. Phys. 129, 184308 (2008)], we focus in this paper on the second excited state. We present theoretical studies of such droplets and films using quantum Monte Carlo approaches. Diffusion and path integral Monte Carlo algorithms combined with a diatomics-in-molecule scheme to model the nonpair additive potential energy surface are used to investigate the energetics and the structure of Rb(∗)He(n) clusters. Helium films as a model for the limit of large clusters are also considered. As in our work on the first electronic excited state, our present calculations find stable Rb(∗)He(n) clusters. The structures obtained are however different with a He-Rb(∗)-He exciplex core to which more helium atoms are weakly attached, preferentially on one end of the core exciplex. The electronic absorption spectrum is also presented for increasing cluster sizes as well as for the film.

International audience; Full-dimensional multiconfigurational time-dependent Hartree calculations on the tunneling splitting of the vibrational ground state and the low lying excited states of malonaldehyde are presented. Methodological developments utilizing the symmetry of double well systems for the efficient calculation of tunneling splittings are described and discussed. Important aspects of the theory underlying the previously communicated results for the ground state tunneling splitting [M. D. Coutinho-Neto et al., J. Chem. Phys. 121, 9207 (2004)] are detailed and further developments facilitating the calculation of tunneling splittings for vibrationally excited states are introduced. Utilizing these developments, the 14 lowest vibrational states of malonaldehyde, i.e., seven tunneling splittings, have been computed. The tunneling splittings are found to vary significantly depending on the particular vibrational excitation. This results in a complex pattern of vibrational levels. Studying the dependence of the tunneling splittings on the vibrational excitation, good agreement with available experimental results is found and intuitive interpretations of the results can be given.

International audience; We present theoretical studies of helium droplets and films doped with one electronically excited rubidium atom Rb( *) ((2)P). Diffusion and path integral Monte Carlo approaches are used to investigate the energetics and the structure of clusters containing up to 14 helium atoms. The surface of large clusters is approximated by a helium film. The nonpair additive potential energy surface is modeled using a diatomic in molecule scheme. Calculations show that the stable structure of Rb( *)He(n) consists of a seven helium atom ring centered at the rubidium, surrounded by a tirelike second solvation shell. A very different structure is obtained when performing a "vertical Monte Carlo transition." In this approach, a path integral Monte Carlo equilibration starts from the stable configuration of a rubidium atom in the electronic ground state adsorbed to the helium surface after switching to the electronically excited surface. In this case, Rb( *)He(n) relaxes to a weakly bound metastable state in which Rb( *) sits in a shallow dimple. The interpretation of the results is consistent with the recent experimental observations [G. Aubock et al., Phys. Rev. Lett. 101, 035301 (2008)].

The determination of the photoelectron spectrum of NH3 and of the internal conversion dynamics of NH3+ recently published [A. Viel, W. Eisfeld, S. Neumann, W. Domcke, U. Manthe, J. Chem. Phys. 124 (2006) 214306] is complemented by the investigation of the effect of the vibrational angular momenta couplings on the dynamics. The multi-configurational time-dependent Hartree method is used to propagate a wave packet on the analytical anharmonic six-dimensional three-sheeted potential energy surface for the ground and first excited states of the ammonia cation. Curvilinear coordinates and the associated quasi-exact kinetic energy operator suitable for the multi-configurational time-dependent Hartree scheme are employed. A non-negligible effect of the use of Cartesian normal modes instead of the curvilinear coordinates is observed on the low energy part of the photoelectron spectrum. However, the three different time scales found in the dynamical calculations for the second absorption band are very similar regardless of the use of either normal modes or curvilinear coordinates. (C) 2007 Elsevier B.V. All rights reserved.

International audience; In this work we present a theoretical and experimental study of the acetylene–hydrogen system. A potential surface considering rigid monomers has been obtained by ab initio quantum chemistry methods. This 4-dimensional potential is further employed to compute, using the close-coupling approach and the coupled-states approximation, pressure broadening coefficients of C2H2 isotropic Raman Q lines over a temperature range of 77 to 2000 K. Experimental data for the acetyleneν2 Raman lines broadened by molecular hydrogen are obtained using stimulated Raman spectroscopy. The comparison of theoretical values with experimental data at 143 K is promising. Approximations to increase the computational efficiency are proposed.

International audience; Quantum dynamics calculations of the ground state tunneling splitting and of the zero point energy of malonaldehyde on the full dimensional potential energy surface proposed by Yagi et al. [J. Chem. Phys. 1154, 10647 (2001)] are reported. The exact diffusion Monte Carlo and the projection operator imaginary time spectral evolution methods are used to compute accurate benchmark results for this 21-dimensional ab initio potential energy surface. A tunneling splitting of 25.7+/-0.3 cm-1 is obtained, and the vibrational ground state energy is found to be 15 122+/-4 cm-1. Isotopic substitution of the tunneling hydrogen modifies the tunneling splitting down to 3.21+/-0.09 cm-1 and the vibrational ground state energy to 14 385+/-2 cm-1. The computed tunneling splittings are slightly higher than the experimental values as expected from the potential energy surface which slightly underestimates the barrier height, and they are slightly lower than the results from the instanton theory obtained using the same potential energy surface.

An analytical anharmonic six-dimensional three-sheeted potential energy surface for the ground and first excited states of the ammonia cation has been developed which is tailored to model the ultrafast photoinduced dynamics. Selected ab initio cuts, obtained by multireference configuration interaction calculations, have been used to determine the parameters of a diabatic representation for this Jahn-Teller and pseudo-Jahn-Teller system. The model includes higher-order coupling terms both for the Jahn-Teller and for the pseudo-Jahn-Teller matrix elements. The relaxation to the ground state is possible via dynamical pseudo-Jahn-Teller couplings involving the asymmetric bending and stretching coordinates. The photoelectron spectrum of NH3 and the internal conversion dynamics of NH+3 have been determined by wave packet propagation calculations employing the multiconfigurational time-dependent Hartree method. Three different time scales are found in the dynamics calculations for the second absorption band. The ultrafast Jahn-Teller dynamics of the two excited states occurs on a 5 A time scale. The major part of the internal conversion to the ground state takes place within a short time scale of 20 fs. This fast internal conversion is, however, incomplete and the remaining excited state population does not decay completely even within 100 fs. (c) 2006 American Institute of Physics.

International audience; The fragmentation dynamics of argon clusters ionized by electron impact is investigated for initial cluster sizes up to n=11 atoms. The dynamics of the argon atoms is modeled using a mixed quantum-classical method in which the nuclei are treated classically and the transitions between electronic states quantum mechanically. The potential-energy surfaces are derived from a diatomics-in-molecules model with the addition of the induced dipole-induced dipole and spin-orbit interactions. The results show extensive and fast fragmentation. The dimer is the most abundant ionic fragment, with a proportion increasing from 66% for n=2 to a maximum of 95% for n=6 and then decreasing down to 67% for n=11. The next abundant fragment is the monomer for n

We present the first prediction for the fragmentation dynamics following electron impact ionization of neutral krypton clusters from 2 to 11 atoms. Fragment proportions and parent ion lifetimes are deduced from a molecular dynamics with quantum transitions study in which the nuclei are treated classically and the transitions between electronic states quantum mechanically. The potential-energy surfaces are derived from a diatomics-in-molecules model to which induced dipole-induced dipole and spin-orbit interactions are added. The results show surprisingly fast and extensive fragmentation for clusters of such a heavy atom, although not as extensive as in the case of neon clusters studied previously [D. Bonhommeau et al., J. Chem. Phys. 123, 54316 (2005)]. The parent ion lifetimes range from 2.8 to 0.7 ps, and the most abundant fragment is Kr(2) (+) for all studied sizes, followed by Kr(+) for sizes smaller than 7 atoms and by Kr(3) (+) for larger sizes. Trimer and larger fragments are found to originate from the lower electronic states of parent ions. The comparison with preliminary results from experiments on size-selected neutral clusters conducted by Steinbach et al. (private communication) reveal a good agreement on the extensive character of the fragmentation. It is checked that the additional internal energy brought by the helium scattering technique used for size selection does not affect the fragment proportions. In addition, the existence of long-lived trajectories is revealed, and they are found to be more and more important for larger cluster sizes and to favor the stabilization of larger fragments. The implications of this work for microsecond-scale dynamics of ionized rare-gas clusters are discussed. In particular, given the extent of fragmentation of the parent clusters and the fast kinetics of the whole process, the small cluster ions that exhibit a monomer loss in the microsecond time window must originate from much larger neutral precursors. The decay rate of the II(12)(u) state of the ionic dimer Kr(2) (+) by spin-orbit coupling is found to be of the order of 3 ps, in contrast to the expected tens of microseconds, but only reasonably faster than the corresponding state of HeNe(+). Finally, the spin-orbit interaction strongly affects both the Kr(+)Kr(2) (+) ratio and some of the characteristic times of the dynamics, especially for smaller sizes, but not the overall dependence of the fragment proportions as a function of cluster size.

The pseudo-Jahn-Teller (PJT) coupling of a nondegenerate state A with a twofold degenerate state E by a degenerate vibrational mode e is studied for a general system with a C(3) main rotational axis. The PJT coupling terms up to sixth order are derived by symmetry considerations for this general (A+E) multiply sign in circle e case. The obtained expression for the 3 x 3 diabatic potential energy matrix is found to be closely related to the expression recently developed for the higher order Jahn-Teller case [A. Viel and W. Eisfeld, J. Chem. Phys. 120, 4603 (2004)]. The dynamical PJT coupling, which can arise for states of appropriate symmetry if one of the vibrational modes induces a change of the nuclear point group between D(3h), C(3v), C(3h), and C(3), is discussed. The effect of the higher order PJT coupling is tested by a two-dimensional model study based on the e bending mode of NH(3)(+). The models are analyzed by fitting the two-dimensional potential energy surfaces. The significance of the higher order terms on the nonadiabatic dynamics is demonstrated by quantum wave packet propagations.

Benchmark calculations of the tunneling splitting in malonaldehyde using the full dimensional potential proposed by Yagi [J. Chem. Phys. 115, 10647 (2001)] are reported. Two exact quantum dynamics methods are used: the multiconfigurational time-dependent Hartree (MCTDH) approach and the diffusion Monte Carlo based projection operator imaginary time spectral evolution (POITSE) method. A ground state tunneling splitting of 25.7+/-0.3 cm(-1) is calculated using POITSE. The MCTDH computation yields 25 cm(-1) converged to about 10% accuracy. These rigorous results are used to evaluate the accuracy of approximate dynamical approaches, e.g., the instanton theory. (C) 2004 American Institute of Physics. (C) 2004 American Institute of Physics.

International audience; We report a theoretical study of the fragmentation dynamics of Ne3+ inside helium nanodroplets,following vertical ionization of the neutral neon trimer. The motion of the neon atoms is treatedclassically, while transitions between the electronic states of the ionic cluster are treated quantummechanically. A diatomics-in-molecules description of the potential energy surfaces is used, in aminimal basis set consisting of three effective p orbitals on each neon atom for the missing electron.The helium environment is modeled by a friction force acting on the neon atoms when their speedexceeds the Landau velocity. A reasonable range of values for the corresponding friction coefficientis obtained by comparison with existing experimental measurements

International audience; The effects of including rotational degrees of freedom on helium solvation densities in molecule-doped helium clusters are investigated for a variety of molecules. Helium densities and cluster energetics are calculated with diffusion Monte Carlo methods. The rotationally induced changes in the helium density distributions are examined and quantified with a theoretical estimator applicable to molecules of arbitrary symmetry. This analysis leads to a discussion of adiabatic following of molecular rotation in a solvating helium environment. We make a detailed comparative study of the effect of molecular rotation as a function of four impurity molecules with varying mass and symmetry: SF6, OCS, HCN, and benzene (C6H6). We find that even for the heaviest rotors, only a fraction of the solvating helium density adiabatically follows the molecular motion in the quantum ground state. For the lightest molecule, HCN, a negligible degree of adiabatic following is found. A discussion of the various definitions is presented to clarify the meaning of adiabatic following, and its applicability to dynamical models of quantum rotation in helium droplets is evaluated in light of the quantitative findings of incomplete adiabatic following established here.

International audience; A six-dimensional analytic potential-energy surface of the three valence states (N,V, Z) of ethene has been constructed on the basis of complete-active-space ab initio calculations and ab initio calculations with perturbation theory of second order based on a complete active reference space. The nuclear coordinate space is spanned by the torsion, the C–C stretch coordinate, the left and right pyramidalization and the symmetric and antisymmetric scissor coordinates. The C–H stretch coordinates and the CH2 rocking angles are kept frozen at their ground-state equilibrium value. A diabatic representation of the valence states of ethene has been constructed within the framework of a Hückel-type model. The diabatic potential-energy elements are represented as analytic functions of the relevant coordinates. The parameters of the analytic functions have been determined by a least-squares fit of the eigenvalues of the diabatic potential-energy matrix to the ab initio data for one-dimensional and two-dimensional cuts of the six-dimensional surface. As a function of the torsion, the analytic potential-energy surface describes the intersections of the V and Z states for torsional angles near 90°, which are converted into conical intersections by the antisymmetric scissor mode. As a function of pyramidalization of perpendicular ethene, it describes the intersections of the diabatic N and Z states, which are converted into conical intersections by displacements in the torsional mode. The analytic potential-energy surfaces can provide the basis for a quantum wave packet description of the internal conversion of photoexcited ethene to the electronic ground state via conical intersections.

The A (1)Sigma(+) potential energy curve of AgH is studied by means of the second-order multistate multireference perturbation theory including the spin-orbit and relativistic effects. The anomalous behavior of the vibrational energy levels observed in experiment is reproduced well by theory. An analysis of the A (1)Sigma(+) wave function shows that at the internuclear distance of 4-6 Angstrom, a partial electron transfer from the 5p(z) orbital of silver to the 1s orbital of hydrogen occurs. This admixture of the ionic-like [core] 4d(10)1s(H)(2) configuration occurring in A (1)Sigma(+) due to two avoided crossings, namely X (1)Sigma(+) with A (1)Sigma(+) and A (1)Sigma(+) with C (1)Sigma(+), is found to be responsible for the unusual shape of the A (1)Sigma(+) potential energy curve: the effective potential is a superposition of a Morse-like covalent interaction between Ag and H, and the electrostatic ionic-like interaction between Ag+ and H-. We present spectroscopic parameters, vibrational levels, and rotational constants computed for a large number of vibrational levels and observe good agreement with available experimental data. The equilibrium distance agrees within 0.01 Angstrom and the vibrational frequency within 60 cm(-1) for the state-specific calculations. Larger relative discrepancy is observed for omega(e)x(e), about 30 cm(-1), however the non-Morse-like nature of the energy curve makes it impossible to describe the levels only with omega and omega(e)x(e), so that direct comparison is not well defined. (Less)

International audience; We present a new method adapted to the calculation of excited rovibrational states of semirigid molecules. It first relies on a description of the molecule in terms of polyspherical coordinates of Jacobi vectors, in order to obtain a compact expression for the kinetic energy operator T̂(q). This general description is then adapted to the molecule considered by defining curvilinear normal modes from the corresponding zero order harmonic Hamiltonian Ĥ0=T̂(qeq) + Vharm(q), the solutions of which are being used as the working basis set. The residual kinetic term ΔT̂ is treated mainly analytically in this basis, and displays no radial contribution. Anharmonic coupling ΔV(q) is handled by means of a pseudospectral scheme based on Gauss Hermite quadratures. This method is particularly adapted to direct iterative approaches which only require the action of Ĥ on a vector, without the need of the associated matrix, thus allowing ultralarge bases to be considered. An application to the excited vibrational states of the HFCO molecule is presented. It is shown in this example that energy levels can be trivially assigned from the leading expansion coefficient of the associated eigenvector.

International audience; Bound energy levels, up to 5000 cm−1 of internal excitation, have been computed for the HFCO molecule. An exact six-dimensional (6D) quantum Hamiltonian, expressed in terms of Jacobi vectors, has been used. It is shown to lead to a compact form of the kinetic energy operator, easy to implement in the calculations. The primary discrete variable representation (DVR) basis set has been contracted by means of the adiabatic pseudospectral method of Friesner et al. [J. Chem. Phys. 99, 324 (1993)]. Two different, global, potential energy surfaces have been considered. The calculated energy levels have been successfully assigned by an automatic labeling procedure. These levels have been compared to the experimental results, providing a test of the accuracy of the existing surfaces.

Parallel implementation of an iterative determination of energy levels of large molecular systems is presented. The basic step consists in acting the Hamiltonian operator H on a wavefunction u , and is achieved by means of a Pseudo Spectral Split Hamiltonian scheme (Leforestier et al., J. Chem. Phys. 106 (1997) 8527). The potential term evaluation V . u , which corresponds by far to the most time consuming part in the sequential code, has been distributed over all the processors. Application to the water dimer (H 2 O) 2 Vibration–Rotation spectrum shows a very good parallel efficiency up to 64 processors.

International audience; Quantum rate calculations for the H+O2→HO+OH+O2→HO+O combustion reaction, as well as for the reverse reaction, are reported. Using the DMBE IV potential energy surface, the cumulative reaction probability N0(E)N0(E) has been directly computed for total angular momentum J=0, by means of the Seideman, Manthe and Miller Lanczos-based absorbing boundary condition method [J. Chem. Phys. 96, 4412 (1992); 99, 3411 (1993)]. Special attention has been paid to the definition of the molecular basis set, and to the sensitivity of the results to the absorbing potentials used in the asymptotic regions. The N0(E) results show very good overall agreement with the coupled channel calculations of Pack et al. [J. Chem. Phys. 102, 5998 (1995)], although the highly oscillatory behavior just above threshold renders such a comparison difficult in that energy range. The behavior of the J≠0 cumulative reaction probability has been estimated from calculations using the Jz-conserving approximation for J values in the range 10–70. This allowed us to define which reference geometry should be used in the J-shifting approximation, in order to compute the cumulative reaction probability NJ(E) for any J value. By imposing conservation of the total energy within this approximation, the rate constants are shown to display better agreement with the experimental results.