Ab Initio Potential Research Articles

Hybrid MP2/MP4 potential surfaces in VSCF calculations of IR spectra: Applications for organic molecules

This study introduces an improved hybrid MP2/MP4 ab initio potential for vibrational spectroscopy calculations which is very accurate, yet without high computational demands. The method uses harmonic vibrational calculations with the MP4(SDQ) potential to construct an improved MP2 potential by coordinate scaling. This improved MP2 potential is used for the anharmonic VSCF calculation. The method was tested spectroscopically for four molecules: butane, acetone, ethylene and glycine. Very good agreement with experiment was found. For most of the systems, the more accurate harmonic treatment considerably improved the MP2 anharmonic results.

Reactive Scattering for Different Isotopologues of the H3– System: Comparison of Different Potential Energy Surfaces

Reaction probabilities and cross sections for the ion-neutral molecule collision H(-) + H2 and its different isotopologues are presented. Quasi-classical trajectory, time-independent, and time-dependent quantum calculations are compared with experimental results. In the calculations, three different ab initio potentials have been used to clarify their applicability.

Three-Dimensional Ab Initio Potential Energy Surface for H–CO(X̃2A′)

We present an ab initio potential for the H-CO(X̃(2)A') complex in which the CO bond length is varied and the long-range interactions between H and CO are accurately represented. It was computed using the spin-unrestricted open-shell single and double excitation coupled cluster method with perturbative triples [RHF-UCCSD(T)]. Three doubly augmented correlation-consistent basis sets were utilized to extrapolate the correlation energy to the complete basis set limit. More than 4400 data points were calculated and used for an analytic fit of the potential: long-range terms with inverse power dependence on the H-CO distance R were fit to the data points for large R, the reproducing kernel Hilbert space (RKHS) method was applied to the data at smaller distances. Our potential was compared with previous calculations and with some data extracted from spectroscopy. Furthermore, it was used in three-dimensional discrete variable representation (DVR) calculations of the vibrational frequencies and rotational constants of HCO, which agree very well with the most recently measured data. Also the dissociation energy D0 = 0.623 eV of HCO into H + CO obtained from these calculations agrees well with experimental values. Finally, we made preliminary two-dimensional (2D) calculations of the cross sections for rotationally inelastic H-CO collisions with the CO bond length fixed and obtained good agreement with recently published 2D results.

Spin-Orbit Suppression of Cold Inelastic Collisions of Aluminum and Helium

We present a quantitative study of suppression of cold inelastic collisions by the spin-orbit interaction. We prepare cold ensembles of >10(11) Al(2P(1/2)) atoms via cryogenic buffer-gas cooling and use a single-beam optical pumping method to measure their magnetic (m(J)-changing) and fine-structure (J-changing) collisions with 3He atoms at millikelvin temperatures over a range of magnetic fields from 0.5 to 6 T. The experimentally determined rates are in good agreement with the functional form predicted by quantum scattering calculations using ab initio potentials. This comparison provides direct experimental evidence for a proposed model of suppressed inelasticity in collisions of atoms in 2P(1/2) states [T. V. Tscherbul et al., Phys. Rev. A 80, 040701(R) (2009)], which may allow for sympathetic cooling of other 2P(1/2) atoms (e.g., In, Tl and metastable halogens).

Spectroscopy of the double minimum 3 3ΠΩ electronic state of 39K85Rb

We report the observation and analysis of the 3 (3)ΠΩ double-minimum electronic excited state of (39)K(85)Rb. The spin-orbit components (0(+), 0(-), 1, and 2) of this state are investigated based on potentials developed from the available ab initio potential curves. We have assigned the vibrational levels v' = 2-11 of the 3 (3)Π1,2 potentials and v' = 2-12 of the 3(3)Π0(+/-) potential. We compare our experimental observations of the 3 (3)ΠΩ state with predictions based on theoretical potentials. The observations are based on resonance enhanced multiphoton ionization of ultracold KRb in vibrational levels v" = 14-25 of the a (3)Σ(+) state. These a-state ultracold molecules are formed by photoassociation of ultracold (39)K and (85)Rb atoms to the 5(1) state of KRb followed by spontaneous emission to the a state.

Interaction potential and gaseous ion mobility of CO+ ions in He

An effective spherical interaction potential for HeCO+ and values for the momentum-transfer collision integral are obtained from experimental ion mobility data by using the direct inversion method. The potential is fitted to a Morse–Spline–van der Waals (MSV) model potential. Consistency is checked by calculating collision integrals and the mobilities of CO+ ions in He gas from the MSV potential and showing that they agree with the experimental data. The separation- and angle-dependent interaction potential energy surface is calculated from the spin-unrestricted, fourth-order Moller–Ploesset theory with single, double, triple and quadruple excitations, using a 6-311++G(3df,3pd) basis set while correcting for basis set superposition error. Full and partial versions of the ab initio potentials are used to determine the transport cross-sections for the collisions of CO+ with He as a function of the collision energy at fixed angles between the C–O bond axis and the internuclear axis. Finally, the transport coefficients of CO+ ions moving through He are calculated accurately, over a wide range of reduced electric field and gas temperature, using an extension of the Monchick–Mason approximation.

IR Spectra of the Water Hexamer: Theory, with Inclusion of the Monomer Bend Overtone, and Experiment Are in Agreement.

Signature IR spectra of isomers of the water hexamer in the spectral range 3000-3800 cm(-1) have been reported by experimentalists, but crucial theoretical interpretation has still not been definitive. Using ab initio potential and dipole moment surfaces and a fully coupled quantum treatment of the intramolecular modes, the ring and book are assigned to spectra obtained in the He nanodroplet and Ar tagging experiments, respectively. The overtone of the intramolecular bend at ca. 3200 cm(-1) is a new calculated feature that completes an important missing piece in previous experimental and theoretical comparisons and leads to a consistent assignment of these two experimental spectra. Calculated IR spectra for the lowest energy forms of the water heptamer and octomer are also presented and compared to experiment. In all the calculated spectra, the bend overtone is demonstrated to be a noticeable feature, and this is one important conclusion from the work. Also, the danger in using scaled double-harmonic spectra to assign spectra is demonstrated.

Nonsequential and Sequential Fragmentation ofCO23+in Intense Laser Fields

We experimentally studied the three-body fragmentation dynamics of CO(2) initiated by intense femtosecond laser pulses. Sequential and nonsequential fragmentations were precisely separated and identified for CO(2)(3+) to break up into O(+) + C(+) + O(+) ions. With accurate measurements of three-dimensional momentum vectors of the correlated atomic ions and calculations of the high-level ab initio potential of CO(2)(3+), we reconstructed the geometric structure of CO(2)(3+) before fragmentation, which turns out to be very close to that of the neutral CO(2) molecule before laser irradiation. Our study indicated that Coulomb explosion is a promising approach for imaging geometric structures of polyatomic molecules if the fragmentation dynamics can be clearly clarified and the appropriate dissociation potential is provided for multiply charged molecular ions.

Absorption spectra of Na atoms in dense He

We present an analysis of Na-He collisional profiles at high density and very low temperature in a unified line shape semi-classical theory which contains the impact as well the quasistatic limits. Clearly understanding the variation of shape of the two fine-structure components of the 3s−3p line with increasing helium density allows us to understand experimental spectra of a Na atom attached to He nanodroplets. We compare our collisional approach to path integral Monte Carlo calculations using the same ab initio Na-He molecular potentials.

Multipole-Based Force Fields from ab Initio Interaction Energies and the Need for Jointly Refitting All Intermolecular Parameters.

Distributed atomic multipole (MTP) moments promise significant improvements over point charges (PCs) in molecular force fields, as they (a) more realistically reproduce the ab initio electrostatic potential (ESP) and (b) allow to capture anisotropic atomic properties such as lone pairs, conjugated systems, and σ holes. The present work focuses on the question of whether multipolar electrostatics instead of PCs in standard force fields leads to quantitative improvements over point charges in reproducing intermolecular interactions. To this end, the interaction energies of two model systems, benzonitrile (BZN) and formamide (FAM) homodimers, are characterized over a wide range of dimer conformations. It is found that although with MTPs the monomer ab initio ESP can be captured better by about an order of magnitude compared to point charges (PCs), this does not directly translate into better describing ab initio interaction energies compared to PCs. Neither ESP-fitted MTPs nor refitted Lennard-Jones (LJ) parameters alone demonstrate a clear superiority of atomic MTPs. We show that only if both electrostatic and LJ parameters are jointly optimized in standard, nonpolarizable force fields, atomic are MTPs clearly beneficial for reproducing ab initio dimerization energies. After an exhaustive exponent scan, we find that for both BZN and FAM, atomic MTPs and a 9-6 LJ potential can reproduce ab initio interaction energies with ∼30% (RMSD 0.13 vs 0.18 kcal/mol) less error than point charges (PCs) and a 12-6 LJ potential. We also find that the improvement due to using MTPs with a 9-6 LJ potential is considerably more pronounced than with a 12-6 LJ potential (≈ 10%; RMSD 0.19 versus 0.21 kcal/mol).

Benchmark problems for mixtures of rarefied gases. I. Couette flow

The planar Couette flow for gaseous mixture He–Ar is calculated by the direct simulation Monte Carlo method based on ab initio potential over the whole range of the gas rarefaction for several values of the mole fraction and for two values of the wall speed. The smaller value of the speed corresponds to the limit when the nonlinear terms are negligible, while the larger value describes a nonlinear flow. The shear stress, velocity gradient, temperature, and mole fraction profiles are presented. The reported results can be used as benchmark data to test model kinetic equations for gaseous mixtures. To study the influence of the intermolecular potential, the same simulations are carried out for the hard sphere molecular model. A relative deviation of the results based on this model from those based on the ab initio potential are analyzed. It is pointed out that the difference between the shear stresses of the two potentials for the linearized solution is within 1%, while it reaches 6% for the nonlinear cases.

Momentum-space calculation of electron—CO elastic collision

We report a momentum-space study on low-energy electron-CO collisions. Elastic differential cross sections (DCS) are obtained using a static-exchange-optical (SEO) model for the incident energies of 2, 3, 5, and 10 eV. Polarization effect of higher reaction channels, including the ionization continuum, on the elastic collision is represented by an ab initio equivalent-local optical potential. The cross sections are compared with experimental measurements and other theoretical results.

Multiparameter model functions in problems of approximating ab initio potentials and spectroscopic data of diatomic molecules

A new multiparameter function of the generalized Morse longrange potential is presented. All earlier similar constructions turn out to be particular cases of this new function. The operation technique for this function is described. Using realistic test examples (ab initio potentials of the K 2 molecule and "experi� mental" spectroscopic data calculated by them), the possibilities of this function are compared with those of the most developed form of the piecewise continuous model potential in problems of direct optimization modeling of potential functions and in problems of optimization modeling of experimental data aiming at determining potentials. A conclusion is drawn that, although the two classes of functions lead, in general, to comparable results in quality, the piecewise continuous approximant permits one to achieve a better repro� duction of the modeled data in some cases. Using the available collection of experimental data, parameters of the piecewise continuous approximant were determined for the potentials of the () and states of the Cs 2 molecule, for which we previously constructed potentials in the form of a generalized Morse func� tion (J. Chem. Phys. 135, 024303 (2011)).

Relation between properties of long-range diatomic bound states

Long-range states of diatomic molecules have average values of internuclear separations $\ensuremath{\langle}R\ensuremath{\rangle}$ at least one order of magnitude larger than the equilibrium value of $R$. For example, the helium dimer ${{}^{4}\mathrm{He}}_{2}$ has a single bound state with $\ensuremath{\langle}R\ensuremath{\rangle}$ of about 50 \AA{}. We show that the properties of these states, such as $\ensuremath{\langle}R\ensuremath{\rangle}$, the dissociation energy, or the $s$-wave scattering length, can be related by simple, yet very accurate, formulas if a potential-energy curve is known. By examining a range of ab initio and empirical helium dimer potentials as well as scaling these potentials, we found that the formulas remain accurate, even if very approximate potentials were used. In addition to ${{}^{4}\mathrm{He}}_{2}$, we present results for ${{}^{9}\mathrm{Be}}_{2},\phantom{\rule{0.28em}{0ex}}{{}^{20}\mathrm{Ne}}_{2}$, and KRb.

Index of refraction of molecular nitrogen for sodium matter waves

We calculate the index of refraction of sodium matter waves propagating through a gas of nitrogen molecules. We use a recent ab initio potential for the ground state of the NaN_2 Van der Waals complex to perform quantal close-coupling calculations and compute the index of refraction as a function of the projectile velocity. We obtain good agreement with the available experimental data. We show that the refractive index contains glory oscillations, but that they are damped by the averaging over the thermal motion of the N_2 molecules. These oscillations appear at lower temperatures and projectile velocity. We also investigate the behavior of the refractive index at low temperature and low projectile velocity to show its dependence on the rotational state of N_2, and discuss the advantage of using diatomic molecules as projectiles.

Simulating liquid water for determining its structural and transport properties

Molecular dynamics simulations are carried out for calculating structural and transport properties of pure liquid water, such as radial distribution functions and self-diffusion and viscosity coefficients, respectively. We employed reparameterized versions of the ab initio water potential by Niesar, Clementi and Corongiu (NCC). In order to investigate the role of the electrostatic contribution, the partial charges of the NCC model are adjusted so that to reproduce the dipole moment values of the SPC/E, SPC/Fw and TIP4P/2005 water models. The single and collective transport coefficients are obtained by employing the Green–Kubo relations at various temperatures. Additionally, in order to overcome convergence difficulties arising from the long correlation times of the stress-tensor autocorrelation functions, a previously reported fitting scheme was employed. The present results indicate that there is a significant relationship between the dipole moment value of the model, and the calculated transport coefficients. We found that by adjusting the molecular dipole moment of the NCC to the value of the TIP4P/2005, the obtained values for the self-diffusion and viscosity coefficients are in better agreement with experiment, compared to the values obtained with the original NCC model. Even though the predictions of the present model exhibits an overall correct behavior, we conclude that further improvements are still required. In order to achieve that, a careful reparameterization of the repulsion–dispersion terms of the potential model is proposed. Also, the effect of the inclusion of many-body effects such as polarizability, should also be investigated.

A simple but accurate potential for the naphthalene-argon complex: Applications to collisional energy transfer and matrix isolated IR spectroscopy

An explicit polarizable potential for the naphthalene-argon complex has been derived assuming only atomic contributions, aiming at large scale simulations of naphthalene under argon environment. The potential was parametrized from dedicated quantum chemical calculations at the CCSD(T) level, and satisfactorily reproduces available structural and energetic properties. Combining this potential with a tight-binding model for naphthalene, collisional energy transfer is studied by means of dedicated molecular dynamics simulations, nuclear quantum effects being accounted for in the path-integral framework. Except at low target temperature, nuclear quantum effects do not alter the average energies transferred by the collision or the collision duration. However, the distribution of energy transferred is much broader in the quantum case due to the significant zero-point energy and the higher density of states. Using an ab initio potential for the Ar-Ar interaction, the IR absorption spectrum of naphthalene solvated by argon clusters or an entire Ar matrix is computed via classical and centroid molecular dynamics. The classical spectra exhibit variations with growing argon environment that are absent from quantum spectra. This is interpreted by the greater fluxional character experienced by the argon atoms due to vibrational delocalization.

Ab initio and DFT analysis of the low-lying electronic states of metal dihalides: quantum chemical calculations on the neutral BrMCl (M = Cu, Ag, Au)

The electronic configuration of the electronic ground and low-lying doublet excited states of neutral metal dihalides BrMCl (M = Cu, Ag, Au) has been investigated on the basis of CASSCF/CASPT2 methods taking into account scalar relativistic effects. A preliminary study of the electronic problem in BrAgCl, based on DFT and CASSCF/CASPT2 approaches and using various basis sets, namely relativistic all-electron basis sets, effective core potentials and ab initio model potentials (AIMP), as well as non-relativistic AIMP is discussed. It is shown that single-determinant methods are not flexible enough to describe the bonding of the neutral species in the electronic ground state regardless of the basis set. The failure to allocate the single electron of BrAgCl correlates with a wrong charge distribution within the complex, which is more accentuated when using pseudopotential basis sets. The inclusion of static and dynamic correlation effects by means of CASSCF/CASPT2 methods using large relativistic all-electron basis sets provides a correct qualitative picture of the electronic structure of the BrMCl series (M = Cu, Ag, Au). The spin unrestricted KS-DFT approach leads to a reasonable description of the degenerate electronic ground state ((2)Σ/(2)Π) bonding in these complexes with negligible spin contamination providing comparative spin densities in the series of molecules under investigation.

Ab initio based large-scale screening of hypothetical MOFs for carbon capture application

ABSTRACTMetal organic frameworks (MOFs) are porous solids that are potential high performance carbon capture materials. We have mined a hypothetical MOF database for structures that have exceptional low-pressure CO2 adsorption properties. We have applied the REPEAT method to generate accurate atomic charges that regenerate the ab initio electrostatic potential. We show that large scale screening at high accuracy is feasible for thousands of structures. We identify promising synthesis targets, like a simple combination of chrysene linker and vanadium inorganic unit, and examine in detail structural features that make better performing MOFs from those that would not be synthesisable. We find that, although screening large numbers of hypothetical structures is necessary to provide experimental targets, there are limitations to the suggestion of using the this database directly for synthesis targets and propose improvements and constraints that should be incorporated into the design of further generations of such a building-block algorithm to reach the accuracy required for high-quality CO2 adsorption simulation.

Coinage metal exciplexes with helium atoms: a theoretical study of M*(2L)Hen (M = Cu, Ag, Au; L = P,D)

The structure and energetics of exciplexes M*((2)L)He(n) (M = Cu, Ag and Au; L = P and D) in their vibrational ground state are studied by employing diffusion Monte Carlo (DMC). Interaction potentials between the excited coinage metals and He atoms are built using the Diatomics-in-Molecule (DIM) approach and ab initio potential curves for the M((2)L)-He dimers. Extending our previous work [Cargnoni et al., J. Phys. Chem. A, 2011, 115, 7141], we computed the dimer potential for Au in the (2)P and (2)D states, as well for Cu and Ag in the (2)D state, employing basis set superposition error-corrected Configuration Interaction calculations. We found that the (2)Π potential correlating with the (2)P state of Au is substantially less binding than for Ag and Cu, a trend well supported by the M(+) ionic radiuses. Conversely, the interaction potentials between a (n - 1)d(9)ns(2 2)D metal and He present a very weak dependency on M itself or the projection of the angular momentum along the dimer axis. This is due to the screening exerted by the ns(2) electrons on the hole in the (n - 1)d shell. Including the spin-orbit coupling perturbatively in the DIM energy matrix has a major effect on the lowest potential energy surface of the (2)P manifold, the one for Cu allowing the formation of a "belt" of five He atoms while the one for Au being completely repulsive. Conversely, spin-orbit coupling has only a weak effect on the (2)D manifold due to the nearly degenerate nature of the diatomic potentials. Structural and energetic results from DMC have been used to support experimental indications for the formation of metastable exciplexes or the opening of non-radiative depopulation channels in bulk and cold gaseous He.