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By extending an earlier study [Gianturco et al., J. Chem. Phys. 154, 054311 (2021)] on the purely rotational excitation of HeH+ by He atoms, we report in this paper integral cross sections and rate coefficients for rovibrational excitation and de-excitation processes in HeH+ due to collisions with He. The data were obtained using a new ab initio potential energy surface that includes the vibrational degree of freedom. The results are compared with those computed using the earlier potential energy surface by Panda and Sathyamurthy [J. Phys. Chem. A 107, 7125 (2003)] that additionally accounts for the proton-exchange reaction between HeH+ and He. It is shown that the exchange channel contributes nearly as much as the inelastic channel to the vibrational excitation and de-excitation processes and that the total rate constants pertaining to the purely inelastic processes are largely of the same magnitude as those obtained when both inelastic and reactive channels are included in the dynamics. The inelastic rovibrational rate coefficients involving this astrophysical cation are also found to be much larger than those obtained for anions present in similar interstellar environments. [ABSTRACT FROM AUTHOR]

A generalized Frenkel–Holstein Hamiltonian is constructed to describe exciton migration in oligo(para-phenylene vinylene) chains, based on excited state electronic structure data for an oligomer comprising 20 monomer units (OPV-20). Time-dependent density functional theory calculations using the ωB97XD hybrid functional are employed in conjunction with a transition density analysis to study the low-lying singlet excitations and demonstrate that these can be characterized to a good approximation as a Frenkel exciton manifold. Based on these findings, we employ the analytic mapping procedure of Binder et al. [J. Chem. Phys. 141, 014101 (2014)] to translate one-dimensional (1D) and two-dimensional (2D) potential energy surface (PES) scans to a fully anharmonic, generalized Frenkel–Holstein (FH) Hamiltonian. A 1D PES scan is carried out for intra-ring quinoid distortion modes, while 2D PES scans are performed for the anharmonically coupled inter-monomer torsional and vinylene bridge bond length alternation modes. The kinetic energy is constructed in curvilinear coordinates by an exact numerical procedure, using the TNUM Fortran code. As a result, a fully molecular-based, generalized FH Hamiltonian is obtained, which is subsequently employed for quantum exciton dynamics simulations, as shown in Paper II [R. Binder and I. Burghardt, J. Chem. Phys. 152, 204120 (2020)]. [ABSTRACT FROM AUTHOR]

The role of vibrational excitation of reactants in driving reactions involving polyatomic species has been often studied by means of classical or quasi-classical trajectory simulations. We propose a different approach based on investigation of vibrational features of the Cl−⋯CH3Cl pre-reaction complex for the Cl− + CH3Cl SN2 reaction. We present vibrational power spectra and frequency estimates for the title pre-reaction complex calculated at the level of classical, semiclassical, and second-order vibrational perturbation theory on a pre-existing analytical potential energy surface. The main goals of the paper are the study of anharmonic effects and understanding of vibrational couplings that permit energy transfer between the collisional kinetic energy and the internal vibrations of the reactants. We provide both classical and quantum pictures of intermode couplings and show that the SN2 mechanism is favored by the coupling of a C–Cl bend involving the Cl− projectile with the CH3 rocking motion of the target molecule. We also illustrate how the routines needed for semiclassical vibrational spectroscopy simulations can be interfaced in a user-friendly way to pre-existing molecular dynamics software. In particular, we present an implementation of semiclassical spectroscopy into the VENUS suite of codes, thus providing a useful computational tool for users who are not experts of semiclassical dynamics. [ABSTRACT FROM AUTHOR]

For molecules with more than three atoms, it is difficult to fit or interpolate a potential energy surface (PES) from a small number of (usually ab initio) energies at points. Many methods have been proposed in recent decades, each claiming a set of advantages. Unfortunately, there are few comparative studies. In this paper, we compare neural networks (NNs) with Gaussian process (GP) regression. We re-fit an accurate PES of formaldehyde and compare PES errors on the entire point set used to solve the vibrational Schrödinger equation, i.e., the only error that matters in quantum dynamics calculations. We also compare the vibrational spectra computed on the underlying reference PES and the NN and GP potential surfaces. The NN and GP surfaces are constructed with exactly the same points, and the corresponding spectra are computed with the same points and the same basis. The GP fitting error is lower, and the GP spectrum is more accurate. The best NN fits to 625/1250/2500 symmetry unique potential energy points have global PES root mean square errors (RMSEs) of 6.53/2.54/0.86 cm−1, whereas the best GP surfaces have RMSE values of 3.87/1.13/0.62 cm−1, respectively. When fitting 625 symmetry unique points, the error in the first 100 vibrational levels is only 0.06 cm−1 with the best GP fit, whereas the spectrum on the best NN PES has an error of 0.22 cm−1, with respect to the spectrum computed on the reference PES. This error is reduced to about 0.01 cm−1 when fitting 2500 points with either the NN or GP. We also find that the GP surface produces a relatively accurate spectrum when obtained based on as few as 313 points. [ABSTRACT FROM AUTHOR]

Quantum molecular dynamics requires an accurate representation of the molecular potential energy surface from a minimal number of electronic structure calculations, particularly for nonadiabatic dynamics where excited states are required. In this paper, we employ pseudospectral sampling of time-dependent Gaussian basis functions for the simulation of non-adiabatic dynamics. Unlike other methods, the pseudospectral Gaussian molecular dynamics tests the Schrödinger equation with N Dirac delta functions located at the centers of the Gaussian functions reducing the scaling of potential energy evaluations from O(N²) to O(N). By projecting the Gaussian basis onto discrete points in space, the method is capable of efficiently and quantitatively describing the nonadiabatic population transfer and intra-surface quantum coherence. We investigate three model systems: the photodissociation of three coupled Morse oscillators, the bound state dynamics of two coupled Morse oscillators, and a two-dimensional model for collinear triatomic vibrational dynamics. In all cases, the pseudospectral Gaussian method is in quantitative agreement with numerically exact calculations. The results are promising for nonadiabatic molecular dynamics in molecular systems where strongly correlated ground or excited states require expensive electronic structure calculations. [ABSTRACT FROM AUTHOR]

Nuclear dynamics in the coupled electronic states of mono-, di-(ortho and meta), and pentafluorobenzene molecules is investigated here. Attempts are specifically made to understand the complexity and broadening of the recorded gas phase electronic absorption spectra of these molecules. Justification is also provided for the low quantum yield of fluorescence emission with increasing number of fluorine substitutions. The nuclear dynamics is simulated from first principles both by time-independent and time-dependent quantum mechanical methods. Potential energy surfaces of the low-lying excited electronic states of these molecules constructed in Paper I [Mondal and Mahapatra, J. Chem. Phys. 133, 084304 (2010)] are employed for the purpose. Theoretical results presented in this paper are compared with the available experimental data and the agreement between the two is found to be excellent. While structured electronic absorption bands are observed for the S1 state of mono- and difluorobenzene molecules, the same for the pentafluorobenzene is broad and structureless. Occurrence of S1-S2 conical intersections in pentafluorobenzene leads to a nonradiative internal conversion of the S1 state in ∼165 fs and contributes to the broadening of the S1←S0 absorption band and a biexponential decay of its fluorescence emission. [ABSTRACT FROM AUTHOR]

Trajectory-based Gaussian basis sets have been tremendously successful in describing highdimensional quantum molecular dynamics. In this paper, we introduce a pseudospectral Gaussianbased method that achieves accurate quantum dynamics using efficient, real-space sampling of the time-dependent basis set. As in other Gaussian basis methods, we begin with a basis set expansion using time-dependent Gaussian basis functions guided by classical mechanics. Unlike other Gaussian methods but characteristic of the pseudospectral and collocation methods, the basis set is tested with N Dirac delta functions, where N is the number of basis functions, rather than using the basis function as test functions. As a result, the integration for matrix elements is reduced to function evaluation. Pseudospectral Gaussian dynamics only requires O(N) potential energy calculations, in contrast to O(N²) evaluations in a variational calculation. The classical trajectories allow small basis sets to sample high-dimensional potentials. Applications are made to diatomic oscillations in a Morse potential and a generalized version of the Henon-Heiles potential in two, four, and six dimensions. Comparisons are drawn to full analytical evaluation of potential energy integrals (variational) and the bra-ket averaged Taylor (BAT) expansion, an O(N) approximation used in Gaussian-based dynamics. In all cases, the pseudospectral Gaussian method is competitive with full variational calculations that require a global, analytical, and integrable potential energy surface. Additionally, the BAT breaks down when quantum mechanical coherence is particularly strong (i.e., barrier reflection in the Morse oscillator). The ability to obtain variational accuracy using only the potential energy at discrete points makes the pseudospectral Gaussian method a promising avenue for on-the-fly dynamics, where electronic structure calculations become computationally significant. [ABSTRACT FROM AUTHOR]

When a nonadiabatic system that has an ionic state (large dipole moment) and a covalent state (small dipole moment) is located in a strong laser field, the crossing point of the two potential energy curves is forced to oscillate due to the oscillating laser field and to meet wavepackets moving on the potential curves many times. This leads to additional transitions between the two states, and under favorable conditions, the wavepacket may be confined in a spatial region rich in nonadiabatic interaction. In this paper, taking the LiF molecule system in a continuous-wave driving field as a prototypical example, the dynamical origins of the wavepacket confinement are theoretically investigated. [ABSTRACT FROM AUTHOR]

A previous calculation for H+N2 [Walch, Duchovic, and Rohlfing, J. Chem. Phys. 90, 3230 (1989)] focused on the minimum energy path (MEP) region of the potential energy surface and on estimates of the lifetime of the HN2 species. In this paper, we report energies computed at geometries selected to permit a global representation of the potential energy surface (PES). As in the previous work, the calculations were performed using the complete active space self-consistent field/externally contracted configuration interaction (CASSCF/CCI) method. The surface was characterized using the same basis set as in the previous paper except that an improved contraction of the H s basis is used. Calculations with a larger basis set were carried out along an approximate MEP obtained with the smaller basis set. The new PES exhibits a sharp curvature, which was not present in the previous calculations, and has a slightly narrower and smaller barrier to dissociation. Saddle points for H atom exchange via collinear and T-shaped HN2 complexes are also reported. [ABSTRACT FROM AUTHOR]

This paper shows how a compact finite difference Hessian approximation scheme can be proficiently implemented into semiclassical initial value representation molecular dynamics. Effects of the approximation on the monodromy matrix calculation are tested by propagating initial sampling distributions to determine power spectra for analytic potential energy surfaces and for 'on the fly' carbon dioxide direct dynamics. With the approximation scheme the computational cost is significantly reduced, making ab initio direct semiclassical dynamics computationally more feasible and, at the same time, properly reproducing important quantum effects inherent in the monodromy matrix and the pre-exponential factor of the semiclassical propagator. [ABSTRACT FROM AUTHOR]

This paper is the first of a two-part series dealing with quantum-mechanical (density-functional-based) studies of helium-mediated deposition of catalytic species on the rutile TiO2(110)-(1×1) surface. The interaction of helium with the TiO2(110)-(1×1) surface is first evaluated using the Perdew-Burke-Ernzerhof functional at a numerical grid dense enough to build an analytical three-dimensional potential energy surface. Three (two prototype) potential models for the He-surface interaction in helium scattering calculations are analyzed to build the analytical potential energy surface: (1) the hard-corrugated-wall potential model; (2) the corrugated-Morse potential model; and (3) the three-dimensional Morse potential model. Different model potentials are then used to study the dynamics upon collision of a 4He300 cluster with the TiO2(110) surface at zero temperature within the framework of a time-dependent density-functional approach for the quantum fluid [D. Mateo, D. Jin, M. Barranco, and M. Pi, J. Chem. Phys. 134, 044507 (2011)] and classical dynamics calculations. The laterally averaged density functional theory-based potential with an added long-range dispersion interaction term is further applied. At variance with classical dynamics calculations, showing helium droplet splashing out of the surface at impact, the time evolution of the macroscopic helium wave-function predicts that the helium droplet spreads on the rutile surface and leads to the formation of a thin film above the substrate. This work thus provides a basis for simulating helium mediated deposition of metallic clusters embedded within helium nanodroplets. [ABSTRACT FROM AUTHOR]

The multi-configuration electron-nuclear dynamics (MCEND) method is a nonadiabatic quantum dynamics approach to the description of molecular processes. MCEND is a combination of the multi-configuration time-dependent Hartree (MCTDH) method for atoms and its antisymmetrized equivalent MCTDHF for electrons. The purpose of this method is to simultaneously describe nuclear and electronic wave packets in a quantum dynamical way, without the need to calculate potential energy surfaces and diabatic coupling functions. In this paper we present first exemplary calculations of MCEND applied to the LiH molecule, and discuss computational and numerical details of our implementation. [ABSTRACT FROM AUTHOR]

The important role of liquid water in many areas of science from chemistry, physics, biology, geology to climate research, etc., has motivated numerous theoretical studies of its structure and dynamics. The significance of quantum effects on the properties of water, however, has not yet been fully resolved. In this paper we focus on quantum dynamical effects in liquid water based on the linearized semiclassical initial value representation (LSC-IVR) with a quantum version of the simple point charge/flexible (q-SPC/fw) model [Paesani et al., J. Chem. Phys. 125, 184507 (2006)] for the potential energy function. The infrared (IR) absorption spectrum and the translational diffusion constants have been obtained from the corresponding thermal correlation functions, and the effects of intermolecular and intramolecular correlations have been studied. The LSC-IVR simulation results are compared with those predicted by the centroid molecular dynamics (CMD) approach. Although the LSC-IVR and CMD results agree well for the broadband for hindered motions in liquid water, the intramolecular bending and O–H stretching peaks predicted by the LSC-IVR are blueshifted from those given by CMD; reasons for this are discussed. We also suggest that the broadband in the IR spectrum corresponding to restricted translation and libration gives more information than the diffusion constant on the nature of quantum effects on translational and rotational motions and should thus receive more attention in this regard. [ABSTRACT FROM AUTHOR]

Classical and quantum mechanical expressions for the j-j′ vector correlation (also referred to as the rotational tilt) are presented for the situation in which the initial and final relative velocity directions are unresolved. The quantum mechanical expressions are compared with previous descriptions in the literature. It is shown that in the case of 2S+1Σ radicals in collision with closed shell species, a tensor opacity formalism can be employed in quasiclassical trajectory calculations to provide classical estimates of both open shell spin-rotation state and nuclear hyperfine state changing (or conserving) cross sections. Polarization parameters are also obtained from the same formalism. The method is applied to calculations on the OH(A 2Σ+)–Ar system using a recently developed potential energy surface. The results of both the closed and open shell quasiclassical trajectory calculations are found to compare favorably with those from close-coupled closed and open shell quantum mechanical scattering calculations. The accompanying paper provides an experimental test of these calculations and of the potential energy surface they employ. [ABSTRACT FROM AUTHOR]

The multistate vibronic dynamics in the X-D electronic states of all three difluorobenzene radical cations are investigated theoretically by an ab initio quantum dynamical approach. The vibronic coupling scheme and the ab initio values of the system parameters are adopted from Paper I [S. Faraji and H. Köppel, J. Chem. Phys. 129, 074310 (2008)]. Extensive calculations by wave-packet propagation have been performed with the aid of the multiconfiguration time-dependent Hartree method. Five coupled electronic potential energy surfaces and 10 (11 in the case of the orthoisomer) vibrational degrees of freedom have been included in these calculations. The nonadiabatic interactions lead to the restructuring of the photoelectron spectral envelopes. Ultrafast internal conversion processes within the electronic manifolds in question demonstrate the strength of the nonadiabatic coupling effects and complement the analogous findings for the electronic spectra. The internal conversion dynamics is characterized by a stepwise transfer of the electronic population to the lowest electronic state on a time scale of femtoseconds to picoseconds. A difference between the three isomers is found to be related to the weaker interaction between the sets of X-Ã and B-C-D states (with high-energy conical intersections) in the meta isomer, as compared to the other isomers. The implications of these findings for the qualitative understanding of the fluorescence dynamics of fluorinated benzene radical cations are discussed. [ABSTRACT FROM AUTHOR]

Several features and the performance of the recently published [P. Jankowski and M. Ziólkowski, Mol. Phys. 104, 2293 (2006)] three-dimensional intermolecular potential energy surface for the Ar–HF complex have been investigated. This full-dimensional surface has been obtained using the method of the local expansion of the exact interaction energy surface [P. Jankowski, J. Chem. Phys. 121, 1655 (2004)] in the Taylor series with respect to intramolecular coordinates. The interaction energies have been calculated with the coupled-cluster supermolecular method with single, double, and noniterative triple excitations. The convergence of the interaction energy with respect to the size of the basis set is discussed. The two-dimensional surfaces resulting from averaging of the full-dimensional surface over the intramolecular vibration of HF have been obtained and directly compared to the empirical H6(4,3,2) set of surfaces proposed by Hutson [J. Chem. Phys. 96, 6752 (1992)]. A very good agreement has been observed. The averaged potentials have been used to calculate the rovibrational energy levels of the Ar–HF and Ar–DF complexes and compared to the experimental data. The accuracy of rovibrational calculations achieved with the new surface is much better than with any of the ab initio surfaces available so far. Predictions of the rovibrational energy levels and spectroscopic constants have also been done for Ar–HF with HF in the v=4,5 vibrational states, and for Ar–DF and DF in the v=3,4 states. The full-dimensional surface studied in this paper is the first ab initio surface which is fully compatible with the empirical H6(4,3,2) surface proposed by Hutson. [ABSTRACT FROM AUTHOR]

In this paper the authors use the optimal internal vibrational coordinates previously determined for the electronic ground state of the ozone molecule to study the vibrational spectrum of the molecule employing the second empirical potential energy surface calculated by Tyuterev et al. [Chem. Phys. Lett. 316, 271 (2000)]. First, the authors compute variationally all the bound vibrational energy levels of the molecule up to the dissociation limit and state the usefulness of the optimal coordinates in this respect, which allows us to converge all the bound levels using relatively small anharmonic basis sets. By analyzing the expansion coefficients of the wave functions, they show then that a large portion of the vibrational spectrum of O3 can be structured in nearly separable polyadic groups characterized by the polyad quantum number N=n1+n2+nθ corresponding to the optimal internal coordinates. Accordingly, they determine an internal effective vibrational Hamiltonian for O3 by fitting the effective Hamiltonian parameters to the experimental vibrational frequencies, using as input parameters in the fit those extracted from an analytical second-order Van Vleck perturbation theory calculation. It is finally shown that the internal effective Hamiltonian thus obtained accurately describes the vibrational spectrum of ozone in the low and medium energy regimes. [ABSTRACT FROM AUTHOR]

We report in this paper a quantum dynamics study for the reaction H+NH3→NH2+H2 on the potential energy surface of Corchado and Espinosa-Garcia [J. Chem. Phys. 106, 4013 (1997)]. The quantum dynamics calculation employs the semirigid vibrating rotor target model [J. Z. H. Zhang, J. Chem. Phys. 111, 3929 (1999)] and time-dependent wave packet method to propagate the wave function. Initial state-specific reaction probabilities are obtained, and an energy correction scheme is employed to account for zero point energy changes for the neglected degrees of freedom in the dynamics treatment. Tunneling effect is observed in the energy dependency of reaction probability, similar to those found in H+CH4 reaction. The influence of rovibrational excitation on reaction probability and stereodynamical effect are investigated. Reaction rate constants from the initial ground state are calculated and are compared to those from the transition state theory and experimental measurement. [ABSTRACT FROM AUTHOR]

In this paper we compare semiclassical initial value representation, conventional transition state theory with Wigner and Eckart tunneling correction, quantum reduced dimensionality, and quasiclassical thermal rate coefficients for N+N2 exchange reaction. [ABSTRACT FROM AUTHOR]

We present several numerical applications based upon the effective-mode formulation for the short-time dynamics through conical intersections in macrosystems, as detailed in the preceding paper and first proposed by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)]. The macrosystem, containing a vast number of nuclear degrees of freedom (modes), is decomposed into a system part and an environment part. Only three effective environmental modes are needed—together with the system’s modes—to accurately calculate the low resolution spectra and the short-time dynamics of the entire macrosystem. For the systems discussed here, results are compared to those of a full quantum wave-packet propagation. Some rules are extracted to provide general tendencies; these rules allow one to understand and predict the dynamical properties in more general situations where the exact quantum dynamics of the macrosystem is out of reach. [ABSTRACT FROM AUTHOR]

The short-time dynamics through a conical intersection of a macrosystem comprising a large number of nuclear degrees of freedom (modes) is investigated. The macrosystem is decomposed into a “system” part carrying a limited number of modes, and an “environment” part. An orthogonal transformation in the environment’s space is introduced, as a result of which a subset of three effective modes can be identified which couple directly to the electronic subsystem. Together with the system’s modes, these govern the short-time dynamics of the overall macrosystem. The remaining environmental modes couple, in turn, to the effective modes and become relevant at longer times. In this paper, we present the derivation of the effective Hamiltonian, first introduced by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)], and analyze its properties in some detail. Several special cases and topological aspects are discussed. [ABSTRACT FROM AUTHOR]

A method for constructing diabatic potential-energy matrices from ab initio quantum chemistry data is described and tested for use in exact quantum reactive scattering. The method is a refinement of that presented in a previous paper, in that it accounts for the presence of the nonremovable derivative coupling. The accuracy of quantum dynamics on this type of diabatic potential is tested by comparison with an analytic model and for an ab initio description of the two lowest-energy states of H3. [ABSTRACT FROM AUTHOR]

In this paper we report a combined experimental and theoretical study on the dynamics of the insertion reaction C(1D)+D2 at 15.5 kJ mol-1 collision energy. Product angular and velocity distributions have been obtained in crossed beam experiments and quasiclassical trajectory (QCT) and rigorous statistical calculations have been performed on the recent and accurate ab initio potential energy surface of Bussery-Honvault, Honvault, and Launay at the energy of the experiment. The molecular-beam results have been simulated using the theoretical calculations. Good agreement between experiment and both QCT and statistical predictions is found. [ABSTRACT FROM AUTHOR]

In this paper effects of higher order Jahn-Teller coupling terms on the nonadiabatic dynamics are studied. Of particular interest is the case when the potential energy surfaces of the degenerate state show pronounced anharmonicity. In order to demonstrate the effects a two-dimensional Exe Jahn-Teller model system is treated which is based on the e[sup ′] stretching vibration of the photoactive [sup 2]E[sup ′] state of NO[sub 3] as a realistic example. The sixth order Exe Jahn-Teller Hamiltonian is derived in the diabatic representation which is valid for any system with a C[sub 3] rotation axis. This diabatization scheme is compared to lower-order Jahn-Teller Hamiltonians and to symmetry adapted as well as ad hoc approximations. Lower-order potentials result in pronounced quantitative and qualitative differences in the dynamics, including differences in the evolution of mean values, the autocorrelation functions (and thus the corresponding spectra), and the electronic population evolution. In the particular example treated, the results of fourth and fifth order potentials are very similar to the sixth order reference system. In contrast, the approximate sixth order Hamiltonians, though the corresponding adiabatic surfaces seem to be nearly identical, results in pronounced differences. The possible consequences for the dynamics of realistic systems with higher dimensionality are briefly discussed. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

This paper presents fully converged integral cross sections for the D[sub 2](j[sub 1]=0,2,4)+OH(j[sub 2]=0,2,4)→HOD+D reaction on the YZCL2 potential energy surface. It is found that the influence of reagent rotation excitation on reactivity is relatively mild compared with that of the D[sub 2] vibration excitation, but is fairly important to the thermal rate constant at low temperature. In general, the OH rotation excitation tends to hinder the reaction, and the D[sub 2] rotation excitation tends to enhance the reactivity. The simultaneous reagent rotation has some correlated effect, with the influence of the D[sub 2] rotation excitation considerably dependent on the OH rotation excitation. It is also found that the reaction is strongly dependent on j[sub 12] (the coupled angular momentum between j[sub 1] and j[sub 2]), K[sub 0] (the projection of the reagent rotation on the body fixed axis), and the parity of the system, in particular for either the OH or D[sub 2] rotationally excited initial states, but this dependence becomes relatively weaker as the collision energy increases. Excellent agreement achieved between theory and experiment on the thermal rate coefficients for temperatures up to 400 K clearly shows that the YZCL2 potential energy surface is capable of producing “quantitatively” accurate results for the title reaction. © 2002 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In this letter we present preliminary results of full six dimensional quantum dynamics calculations for dissociative adsorption of a hydrogen molecule on a Cu(111) surface. We utilize the time-dependent wave-packet approach to simulate the dissociation process on a full dimensional LEPS potential energy surface which has incorporated the latest ab initio data [Hammer et al. Phys. Rev. Lett. 73, 1400 (1994)]. We use a novel partitioning of the angular momentum operator in the split-operator method so that a direct product DVR can be rigorously implemented. The most interesting observation in the present rigorous quantum dynamics study is the site-averaged effect, i.e., the averaged dissociation probability of the four dimensional calculations over the three symmetric impact sites strongly resembles the exact dissociation probability of the six dimensional calculations. In accord with the low dimensional calculations, initial vibrational excitation of H2 effectively reduces the translational threshold energy. The rotational orientation effect observed in the four dimensional studies remains in the present full dimensional dynamics with the cartwheel orientation yielding dramatically lower dissociative efficiency than the energetically equivalent helicopter orientation. We focus on normal incident scattering. The diffractive scattering and more detailed results will be presented in a later paper.. [ABSTRACT FROM AUTHOR]

Classical transition state theory (TST) provides the rigorous basis for the application of molecular dynamics (MD) to infrequent events, i.e., reactions that are slow due to a high energy barrier. The TST rate is simply the equilibrium flux through a surface that divides reactants from products. In order to apply MD to infrequent events, corrections to the TST rate that account for recrossings of the dividing surface are computed by starting trajectories at the dividing surface and integrating them backward and forward in time. Both classical TST and conventional MD invoke the adiabatic approximation, i.e., the assumption that nuclear motion evolves on a single potential energy surface. Many chemical rate processes involve multiple potential energy surfaces, however, and a number of ‘‘surface-hopping’’ MD methods have been developed in order to incorporate nonadiabatic transitions among the potential energy surfaces. In this paper we generalize TST to processes involving multiple potential energy surfaces. This provides the framework for a new method for MD simulation of infrequent events for reactions that evolve on multiple potential energy surfaces. We show how this method can be applied rigorously even in conjunction with phase-coherent surface-hopping methods, where the probability of switching potential energy surfaces depends on the history of the trajectory, so integrating trajectories backward to calculate the recrossing correction is problematic. We illustrate this new method by applying it in conjunction with the ‘‘molecular dynamics with quantum transitions’’ (MDQT) surface-hopping method to a one-dimensional two-state barrier crossing problem. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The routine location of the global minimum energy structures of a molecular system remains a challenging problem in chemical physics. Recently Straub and co-workers [J. Ma et al., J. Chem. Phys. 99, 4024 (1993) and 101, 533 (1994)] have introduced a number of novel dynamic simulated annealing algorithms for global optimization. Instead of using Newton’s equations, they are based on Liouville’s equation and the particles are described with phase space distributions. The methods were shown to have significantly enhanced effectiveness over traditional methods when used to locate the global minima of Lennard-Jones clusters. In this paper the extensions necessary to use these methods with ab initio quantum mechanical potentials are presented and their application is illustrated by the simulated annealing of a small lithium atom cluster. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Potential energy surfaces have been determined for the A’ and A‘ states of the He(1S)+CH(X 2Π) system. The interaction energies were computed using a Hartree–Fock singles and doubles CI treatment; convergence of the calculation with respect to both basis set and configuration set was investigated. The surfaces have been represented quantitatively by standard Legendre polynomial expansions and qualitatively by novel pairwise additive potentials. With the pairwise additive models, successful fits require that the centers of force be orbital based as opposed to the typical nucleus-based form. Comparison of the surfaces would suggest that the final fitted surfaces are accurate to a few tenths of a kcal/mol up to 5–10 kcal/mol. In the following paper, the dynamical consequences of the small differences between all the surfaces will be assessed by quantum dynamics calculations of cross sections and their subsequent comparison to experiment. [ABSTRACT FROM AUTHOR]

We develop a theory and the method of its application for chemical dynamics in systems, in which the adiabatic potential energy hyper-surfaces (PES) are densely quasi-degenerate to each other in a wide range of molecular geometry. Such adiabatic electronic states tend to couple each other through strong nonadiabatic interactions. Technically, therefore, it is often extremely hard to accurately single out the individual PES in those systems. Moreover, due to the mutual nonadiabatic couplings that may spread wide in space and due to the energy-time uncertainty relation, the notion of the isolated and well-defined potential energy surface should lose the sense. On the other hand, such dense electronic states should offer a very interesting molecular field in which chemical reactions to proceed in characteristic manners. However, to treat these systems, the standard theoretical framework of chemical reaction dynamics, which starts from the Born-Oppenheimer approximation and ends up with quantum nuclear wavepacket dynamics, is not very useful. We here explore this problem with our developed nonadiabatic electron wavepacket theory, which we call the phase-space averaging and natural branching (PSANB) method [T. Yonehara and K. Takatsuka, J. Chem. Phys. 129, 134109 (2008)], or branching-path representation, in which the packets are propagated in time along the non-Born-Oppenheimer branching paths. In this paper, after outlining the basic theory, we examine using a one-dimensional model how well the PSANB method works with such densely quasi-degenerate nonadiabatic systems. To do so, we compare the performance of PSANB with the full quantum mechanical results and those given by the fewest switches surface hopping (FSSH) method, which is known to be one of the most reliable and flexible methods to date. It turns out that the PSANB electron wavepacket approach actually yields very good results with far fewer initial sampling paths. Then we apply the electron wavepacket dynamics in path-branching representation and the so-called semiclassical Ehrenfest theory to a hydrogen molecule embedded in twelve membered boron cluster (B12) in excited states, which are densely quasi-degenerate due to the vacancy in 2p orbitals of boron atom [1s22s22p1]. Bond dissociation of the hydrogen molecule quickly takes place in the cluster and the resultant hydrogen atoms are squeezed out to the surface of the cluster. We further study collision dynamics between H2 and B12, which also gives interesting phenomena. The present study suggests an interesting functionality of the boron clusters. [ABSTRACT FROM AUTHOR]

Due to the behavior of the pseudo-orbitals near nuclei, basis set selection in shape-consistent effective potential calculations can be problematic in studies using correlation techniques based on virtual orbital expansions (configuration interaction, etc.). In this paper we quantify the magnitude of the problem and give simple rules for the selection of correlating functions in a manner that parallels the use of simple diffuse primitives in all-electron work. Our calculations show the problem to be substantial for s and p basis sets, and to involve both one- and two-center effects, but is negligible for higher l. We also show that the problems can be avoided by the inclusion of one additional high exponent s primitive in the basis set and by augmenting p primitives with a higher exponent function so as to give zero first derivatives at the nucleus. By this recipe, computed s and p shell correlation energies in single and double promotion configuration interaction calculations can be increased by 3%-7%, as compared to basis sets using simple diffuse primitives for correlation. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]