Ab Initio Potential Research Articles

Theoretical predictions on the role of the internal H3+ rotation in the IR spectra of the H5+ and D5+ cations

The IR spectra of the H5(+) and D5(+) cations in the mid- and far-IR spectral regions have been recently reported by experimentalists. These spectra show very rich vibrational patterns representing a challenge for state-of-the-art theoretical methods to provide definitive interpretations of them. Using a full-dimensional quantum anharmonic treatment, within the MCTDH approach, together with ab initio potential and dipole moment surfaces, the predominant features in the spectra are assigned, completing an important part in previous theoretical and experimental comparisons. The internal rotation of the H3(+) unit by exciting the H3(+)-H2 stretching mode is found to correspond to the new calculated features at 1182, 1876, and 2139 cm(-1) of the H5(+) spectrum, leading to a consistent assignment with the experimental spectra. In the calculated spectra of both H5(+) and D5(+) clusters, the progressions in the H3(+)-H2 stretch of the shared proton and the in- and out-of- plane H3(+) rotation are demonstrated to be the main features. Such states are expected to play a central role in the low temperature hydrogen/deuterium proton hop/exchange H3(+) + H2 reactions.

Multipoles as Force Field Parameters - Accuracy and Redundancy

Simulation of proteins and other large biomolecules rely on a force field representation of the potential energy surface. Fixed charge force fields, like AMBER, CHARMM, OPLS, and GROMOS, are widely used, however, it is well known that they, due to their simplicity provide an inaccurate description of the electrostatic energy component.In this study, multipoles up to quadrupoles are fitted to reproduce an ab initio electrostatic potential. The accuracy gained by introducing higher order multipoles is significant. However, the inclusion of multipoles as electrostatic parameters is highly associated with additional redundancy among the parameters. In an attempt to resolve redundancy, a large fraction of less important multipoles were identified and eliminated, without affecting the accuracy of the electrostatic potential. Furthermore, it is concluded that the reduced set of chemically important multipoles is transferable to different geometries of the same molecule. This is a promising result with respect to force field development, which highly relies on the assumption of transferability.

Experimental and theoretical investigation of correlated fine structure branching ratios arising from state-selected predissociation of BrO (A2Π3/2)

We present results for the v'-dependent predissociation dynamics of the BrO (A(2)Π3/2) state using velocity map ion imaging. Correlated fine structure branching ratios, Br((2)P(J)) + O((3)P(J)), have been measured for v' = 5-16 states. The experimental branching ratios are non-statistical and strongly dependent on the initial vibronic state. The current measurements represent an extensive dataset containing rich information about the predissociation dynamics of this system and should provide a stringent test for modern theory. New high level ab initio excited state potentials are presented and have been optimized using experimental v'-dependent predissociation lifetimes and calculated coupling constants. Comparisons between the experimental branching ratios and the predictions based on diabatic and adiabatic limiting models are presented. We find that the adiabatic model is most consistent with the observed trends in the correlated branching ratios, in contrast to previous studies on the related ClO system.

Carbon Dioxide Hydrate Phase Equilibrium and Cage Occupancy Calculations Using Ab Initio Intermolecular Potentials

Gas hydrate deposits are receiving increased attention as potential locations for CO2 sequestration, with CO2 replacing the methane that is recovered as an energy source. In this scenario, it is very important to correctly characterize the cage occupancies of CO2 to correctly assess the sequestration potential as well as the methane recoverability. In order to predict accurate cage occupancies, the guest–host interaction potential must be represented properly. Earlier, these potential parameters were obtained by fitting to experimental equilibrium data and these fitted parameters do not match with those obtained by second virial coefficient or gas viscosity data. Ab initio quantum mechanical calculations provide an independent means to directly obtain accurate intermolecular potentials. A potential energy surface (PES) between H2O and CO2 was computed at the MP2/aug-cc-pVTZ level and corrected for basis set superposition error (BSSE), an error caused due to the lower basis set, by using the half counterpoise method. Intermolecular potentials were obtained by fitting Exponential-6 and Lennard-Jones 6-12 models to the ab initio PES, correcting for many-body interactions. We denoted this model as the “VAS” model. Reference parameters for structure I carbon dioxide hydrate were calculated using the VAS model (site–site ab initio intermolecular potentials) as Δμ(w)(0) = 1206 ± 2 J/mol and ΔH(w)(0) = 1260 ± 12 J/mol. With these reference parameters and the VAS model, pure CO2 hydrate equilibrium pressure was predicted with an average absolute deviation of less than 3.2% from the experimental data. Predictions of the small cage occupancy ranged from 32 to 51%, and the large cage is more than 98% occupied. The intermolecular potentials were also tested by calculating the pure CO2 density and diffusion of CO2 in water using molecular dynamics simulations.

Ab initio simulation of heat transfer through a mixture of rarefied gases

The heat flux problem for a binary gaseous mixture confined between two parallel plates with different temperatures is studied on the basis of the direct simulation Monte Carlo method with an implementation of ab initio potential. The calculations were carried for a wide range of the gas rarefaction, for several values of the mole fraction and for two values of the temperature difference. The smaller value of the difference corresponds to the limit when the nonlinear terms are negligible, while the larger value describes a nonlinear heat transfer. The heat flux, temperature, and mole fraction distributions are presented. 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 is analyzed. It is pointed out that the difference between the heat flux of the two potentials is about 8% and 5% for the small and large temperature differences, respectively. The temperature distribution between plates is weakly affected by the molecular potential, while the chemical composition variation is the most sensitive quantity for the considered problem. The reported results can be used as benchmark data to test model kinetic equations for gaseous mixtures.

Spectroscopic observation of higher vibrational levels of C2 through visible band systems

Higher vibrational levels of the C2 molecule than those observed so far were investigated for the X(1)Σ(g)(+), A(1)Π(u), a(3)Π(u), c(3)Σ(u)(+), and d(3)Π(g) states through the Phillips, Swan, and d(3)Π(g)-c(3)Σ(u)(+) band systems under a jet-cooled condition. The term values and the molecular constants for 21 new vibronic levels were determined from rotationally resolved excitation spectra. The determined term values and rotational constants were compared to those derived from high-level ab initio potential curves. Perturbations identified in low J levels of the d(3)Π(g) (v = 8) state are most likely to be caused by the 1(5)Π(g) (v = 3) state.

Classical Trajectory Study of Energy Transfer in Collisions of Highly Excited Allyl Radical with Argon

Predicting the results of collisions of polyatomic molecules with a bath of atoms is a research area that has attracted substantial interest in both experimental and theoretical chemistry. Energy transfer, which is the consequence of such collisions, plays an important role in gas-phase kinetics and relaxation of excited molecules. We present a study of energy transfer in single collisions of highly vibrationally excited allyl radical in argon. We evolve a total of 52 000 classical trajectories on a potential energy surface, which is the sum of an ab initio intramolecular potential for the allyl and a pairwise interaction potential describing the argon's effect on the allyl. The former is described by means of a permutationally invariant full-dimensional potential, whereas the interaction potential between allyl and argon is obtained by means of a sum of pairwise potentials dependent on nonlinear parameters that have been fit to a set of MP2/avtz counterpoise corrected ab initio energies. Results are reported for energy transfers and related probability densities at different collisional energies. The sensitivity of results to the interaction potential is considered and the potential is shown to be suitable for future applications involving different isomers of the allyl. The impact of highly efficient collisions in the energy transfer process is examined.

Deriving Static Atomic Multipoles from the Electrostatic Potential

The description of molecular systems using multipolar electrostatics calls for automated methods to fit the necessary parameters. In this paper, we describe an open-source software package that allows fitting atomic multipoles (MTPs) from the ab initio electrostatic potential by adequate atom typing and judicious assignment of the local axis system. By enabling the simultaneous fit of several molecules and/or conformations, the package addresses issues of parameter transferability and lack of sampling for buried atoms. We illustrate the method by studying a series of small alcohol molecules, as well as various conformations of protonated butylamine.

Inelastic aluminium-hydrogen collision data for non-LTE applications in stellar atmospheres

Aims. Inelastic processes in low-energy Si + H and Si+ + H− collisions are treated for the states from the ground state up to the ionic state, in order to provide rate coefficients needed for non-LTE modeling of Si in cool stellar atmospheres.Methods. Electronic molecular structure is determined using a recently proposed model approach based on an asymptotic method in combination with available ab initio potentials. Nonadiabatic nuclear dynamics are treated by means of a combination of multichannel formulas and the branching-probability-current method, based on the Landau-Zener model for nonadiabatic transition probabilities.Results. Cross sections and rate coefficients for inelastic processes in Si + H and Si+ + H− collisions for all transitions between 26 low-lying states plus the ionic state are calculated. It is shown that the highest rate coefficient values correspond to the excitation, de-excitation, ion-pair formation, and mutual neutralization processes involving the Si(3p4p 3 D), Si(3p3d 3 F), Si(3p4p 1 D), Si(3p3d 3 P), Si(3p4p 1 S), and the ionic Si+ + H− states. These processes are likely to be important in non-LTE modeling.

Theoretical Study on the Rotational Spectra of Ar-D232S Complex

We report a theoretical study on the rotational spectra of Ar-D232S. The intermolecular potential energy surface was transformed from our latest ab initio three-dimensional potential of Ar-H232S. The rotational energy levels and wavefunctions of the complex were calculated by using the radial discrete variable representation/angular finite basis representation method and the Lanczos algorithm. The calculated rotational transition frequencies and structural parameters were found to be in good agreement with the available experimental values.

Hyperfine and vibrational structure of weakly bound levels of the lowest1gstate of molecular87Rb2

Photoassociation resonances in the ${}^{87}$Rb${}_{2}$ ${1}_{g}$ state dissociating to $5{\phantom{\rule{0.16em}{0ex}}}^{2}S+5{}^{2}{P}_{1/2}$ were produced by the excitation of colliding ${}^{87}$Rb atoms in a far-off resonance trap. Levels down to 31 cm${}^{\ensuremath{-}1}$ below the dissociation limit were measured with resonance linewidths of 15 to 20 MHz, and have been located to a one-sigma combined systematic and statistical uncertainty of 50 MHz relative to the $5{\phantom{\rule{0.16em}{0ex}}}^{2}S+5{}^{2}{P}_{1/2}$ limit. Electron and nuclear spins were fixed to a space-fixed axis by circularly polarized optical pumping, so that only states with total nuclear spin $I=3$ were excited, thereby greatly simplifying the spectrum. The analysis of the data yielded hyperfine coupling parameters $A(v)$, vibrational $G(v)$, and rotational $B(v)$ parameters. The $G(v)$ parameters could be fit to an rms accuracy of about 0.01 cm${}^{\ensuremath{-}1}$ to a potential constructed from current ${C}_{3}$ and ${C}_{6}$ long-range dispersion parameters plus an ab initio potential that was adjusted in depth and with quadratic terms in the internuclear distance added to the inner wall.

Isomerization and Decomposition of a Criegee Intermediate in the Ozonolysis of Alkenes: Dynamics Using a Multireference Potential

The isomerization and decomposition dynamics of the simplest Criegee intermediate CH2 OO have been studied by classical trajectory simulations using the multireference ab initio MR-PT2 potential on the fly. A new, accelerated algorithm for dynamics with MR-PT2 was used. For an initial temperature of 300 K, starting from the transition state from CH2 OO→CH2 O2 , the system reaches the dioxirane structure in around 50 fs, then isomerizes to formic acid (in ca. 2800 fs), and decomposes into CO+H2 O at around 2900 fs. The contributions of different configurations to the multiconfigurational total electronic wave function vary dramatically along the trajectory, with diradical contributions being important for transition states corresponding to H-atom transfers, while being only moderately significant for CH2 OO. The implications for reactions of Criegee intermediates are discussed.

Isomerization and Decomposition of a Criegee Intermediate in the Ozonolysis of Alkenes: Dynamics Using a Multireference Potential

The isomerization and decomposition dynamics of the simplest Criegee intermediate CH2OO have been studied by classical trajectory simulations using the multireference ab initio MR-PT2 potential on the fly. A new, accelerated algorithm for dynamics with MR-PT2 was used. For an initial temperature of 300 K, starting from the transition state from CH2OO→CH2O2 , the system reaches the dioxirane structure in around 50 fs, then isomerizes to formic acid (in ca. 2800 fs), and decomposes into CO+H2O at around 2900 fs. The contributions of different configurations to the multiconfigurational total electronic wave function vary dramatically along the trajectory, with diradical contributions being important for transition states corresponding to H-atom transfers, while being only moderately significant for CH2OO. The implications for reactions of Criegee intermediates are discussed.

The molecular structure of and interconversion tunneling in the argon-cis-1,2-difluoroethylene complex

Guided by ab initio predictions, the structure of the gas-phase complex formed between cis-1,2-difluoroethylene and an argon atom in a pulsed molecular jet is determined using microwave spectroscopy in the 5.7-21.5 GHz region of the spectrum. This is a non-planar, symmetric species, with the argon atom located in the FCCF cavity of the difluoroethylene. The transitions in the microwave spectrum are observed to be split by an interconversion tunneling motion between the two equivalent configurations for the complex with the argon atom located either above or below the difluoroethylene molecular plane. Both one- and two-dimensional discrete variable representation calculations of the tunneling splitting using the ab initio interaction potential for the complex suggest that the barrier to interconversion is overestimated by theory.

Ab initio theoretical study of the [formula omitted] and 4f75d manifolds of Tb3+-doped BaF2 cubic sites

An ab initio model potential embedded cluster study on the 4f8 and 4f7 5d manifolds of the long range compensated, cubic, substitutional Tb3+ defects of Tb-doped BaF2 is presented here. 4f–4f and 4f–5d transition energies and 4f–5d absorption electric dipole oscillator strengths for the dipole allowed transitions are reported and comparisons with emission and excitation experimental spectra are presented. We find good agreement with the energies of the experimental 4f–4f green and blue emissions. The characteristic features of the 4f–5d excitation spectrum (spin allowed vs. spin forbidden transitions) are well reproduced by the calculations. The transition energies from the ground state to the different spin nonet and spin septet levels of the 4f7 5d configuration of this ion in the center of the lanthanide series show an error of around 10%, which is in line with previous calculations on other lanthanide ions with lower spin multiplicities and simpler manifolds at the beginning and at the end of the series. The calculation supports a recent assignment of experimental excitation bands between 54,000 and 66,000cm−1 as 4f→5d(t2g) transitions. On the other hand, a new assignment is made of the highest band in the excitation spectrum at around 76,000cm−1: it corresponds to transitions to levels of the 4f7 5d configuration with the 4f7 subshell in the excited 6P term, rather than to a Tb-bound exciton. Preliminary studies on excitonic states of Tb-doped BaF2 indicate that energy levels that can be characterized as Tb-trapped excitons are found in the same spectral region as the spin forbidden 4f→5d(t2g) transitions at ground state Tb–F distances, and their energy lowers very much at shorter Tb–F distances.

Calculations and measurements of the deuterium tunneling frequency in the propiolic acid-formic acid dimer and description of a newly constructed Fourier transform microwave spectrometer

The concerted proton tunneling frequency for the propiolic acid-formic acid dimer was calculated using a relaxed ab initio double-well potential in the imaginary-frequency mode of the saddle point, and new measurements were made for the deuterated propiolic acid-formic acid (ProOD-FAOD) isotopologue. It is important to have consistent calculated tunneling frequency values between normal and deuterated isotopologues since parameters can be readily adjusted to get good agreement with one isotopologue. High-resolution rotational spectra of deuterated (ProOD-FAOD) dimer were measured using a newly constructed Fourier Transform microwave spectrometer. The new spectrometer has mirror size: 30 cm in diameter with a radius of curvature of 59 cm and is equipped with multiple-FID data collection (5-10 FID's for each gas pulse). For the deuterated (ProOD-FAOD) isotopologue, 45 rotational lines (a type: 34; b type: 11) were measured in the lowest tunneling states range between 6.5 GHz and 15.5 GHz. With the new high-resolution measurements of the tunneling doublets (b-dipole transitions), the double potential well responsible for the deuterium tunneling was depicted much more precisely. The two tunneling states are separated by 3.48 MHz. The rotational constants obtained in this work are quite helpful for further structure analysis as well.

Potential energy function for HeS+ and transport properties of S+ in He

The interaction potential energy curve for HeS+ is obtained directly from experimental ion mobility values and by ab initio calculations. The potentials are compared to similar results for HeS−. It is concluded that the experimentally-inferred potential may be more accurate than the ab initio potential because spin–orbit interactions have not been included in the latter.

Zeeman relaxation induced by spin-orbit coupling in cold antimony-helium collisions

We investigate Zeeman relaxation in cold Sb(${}^{4}{S}_{3/2}^{\ensuremath{\circ}}$)--He collisions in a magnetic field. Ensembles of $g$${10}^{13}$ laser-ablated Sb atoms are cooled in cryogenic ${}^{4}$He buffer gas to 800 mK and inelastic collisions are observed to equilibrate the ${m}_{J}$-state distribution to the translational temperature. The ratio $\ensuremath{\gamma}$ of momentum transfer to inelastic collision rates is measured to be $\ensuremath{\leqslant}9.1\ifmmode\times\else\texttimes\fi{}{10}^{2}$. We also perform quantum scattering calculations of Sb--${}^{4}$He collisions, based on ab initio interaction potentials, that demonstrate significant anisotropy of the ground state induced by the spin-orbit interaction. Agreement is obtained between theory and experiment with a $\ensuremath{\approx}$10$%$ increase in the ab initio potential depth. This work suggests that buffer-gas-cooled pnictogen atoms lighter than Sb can be loaded into a magnetic trap.

Atomistic simulation for ordered Ho3Fe29−xCrx and disordered Ho2Fe17 intermetallic compounds

The structural properties of intermetallic Ho3Fe29−xCrx have been studied by using ab initio pair potentials obtained by the lattice inversion method. Calculated results show that in Ho3Fe29−xCrx, the order of site preference is 4g(Fe6), 4i(Fe3) and 4i(Fe2), and the calculated lattice constants coincide quite well with experimental values. The evolution process from ordered Ho3Fe29 to disordered Ho2Fe17 (Th2Ni17-type) is evaluated. The structural properties of the disordered Ho2Fe17 compound, including lattice constants and X-ray diffraction have been calculated, and the lattice constants are in good agreement with experiments.

Polarized Protein-Specific Charges from Atoms-in-Molecule Electron Density Partitioning

Atomic partial charges for use in traditional force fields for biomolecular simulation are often fit to the electrostatic potentials of small molecules and, hence, neglect large-scale electronic polarization. On the other hand, recent advances in atoms-in-molecule charge derivation schemes show promise for use in flexible force fields but are limited in size by the underlying quantum mechanical calculation of the electron density. Here, we implement the density derived electrostatic and chemical charges method in the linear-scaling density functional theory code ONETEP. Our implementation allows the straightforward derivation of partial atomic charges for systems comprising thousands of atoms, including entire proteins. We demonstrate that the derived charges are chemically intuitive, reproduce ab initio electrostatic potentials of proteins and are transferable between closely related systems. Simulated NMR data derived from molecular dynamics of three proteins using force fields based on the ONETEP charges are in good agreement with experiment.