Potential energy surfaces of ozone in the ground state

Equilibrium parameters of ozone, such as equilibrium geometry structure parameters, force constants and dissociation energy are presented by CBS-Q ab initio calculations. The calculated equilibrium geometry structure parameters and energy are in agreement with the corresponding experimental values. The potential energy function of ozone with a C2v symmetry in the ground state is described by the simplified Sorbie-Murrell many-body expansion potential function according to the ozone molecule symmetry. The contour of bond stretching vibration potential of an O3 in the ground state, with a bond angle （θ） fixed, and the contour of O3 potential for O rotating around O1-O （R1）, with O1-O bond length taken as the one at equilibrium, are plotted. Moreover, the potentials are analysed.

Ab initio potential energy surface and anharmonic vibration spectrum of NF_(3)^(+)

Potential energy surfaces(PESs), vibrational frequencies, and infrared spectra are calculated for NF_(3)^(+) using ab initio calculations, based on UCCSD(T)/cc-p VTZ combined with vibrational configuration interaction(VCI). Based on an iterative algorithm, the surfaces(SURF) program adds automatic points to the lattice representation of the potential function, the one-dimensional and two-dimensional PESs are calculated after reaching a convergence threshold, finally the smooth image of the potential energy surface is fitted. The PESs accurately account for the interaction between the different modes, with the mode q_(6) symmetrical stretching vibrations having the greatest effect on the potential energy change of the whole system throughout the potential energy surface shift. The anharmonic frequencies are obtained when the VCI matrix is diagonalized. Fundamental frequencies, overtones, and combination bands of NF_(3)^(+) are calculated, which generate the degenerate phenomenon between their frequencies. Finally, the calculated anharmonic frequency is used to plot the infrared spectra.Modal antisymmetric stretching ν_(5) and symmetric stretching ν_(6) exhibit a phenomenon of large-intensity borrowing. This study can provide data to support the characterization in the laboratory.

Ground state properties and potential energy surfaces of 270Hs from multidimensionally-constrained relativistic mean field model

We study the ground state properties,potential energy curves and potential energy surfaces of the superheavy nucleus 270Hs by using the multidimensionally-constrained relativistic mean-field model with the efFective interaction PC-PK1.The binding energy,size and shape as well as single particle shell structure corresponding to the ground state of this nucleus are obtained.270Hs is well deformed and exhibits deformed doubly magic feature in the single neutron and proton level schemes.One-dimensional potential energy curves and two-dimensional potential energy surfaces are calculated for 270Hs with various spatial symmetries imposed.We investigate in detail the effects of the reflection asymmetric and tri axial distortions on the fission barrier and fission path of 270Hs.When the axial symmetry is imposed,the reflection symmetric and reflection asymmetric fission barriers both show a double-hump structure and the former is highe匚However,when tri axial shapes are allowed the reflection symmetric barrier is lowered very much and then the reflection symmetric fission path becomes favorable.

Calculation of multidimensional potential energy surfaces for even-even transuranium nuclei: systematic investigation of the triaxiality effect on the fission barrier

Static fission barriers for 95 even-even transuranium nuclei with charge number Z = 94-118 have been systematically investigated by means of pairing self-consistent Woods-Saxon-Strutinsky calculations using the potential energy surface approach in multidimensional（β;, γ, β;） deformation space. Taking the heavier （252）;f nucleus（with the available fission barrier from experiment） as an example, the formation of the fission barrier and the influence of macroscopic, shell and pairing correction energies on it are analyzed. The results of the present calculated β;values and barrier heights are compared with previous calculations and available experiments. The role of triaxiality in the region of the first saddle is discussed. It is found that the second fission barrier is also considerably affected by the triaxial deformation degree of freedom in some nuclei（e.g., the Z =112-118 isotopes）. Based on the potential energy curves, general trends of the evolution of the fission barrier heights and widths as a function of the nucleon numbers are investigated. In addition, the effects of Woods-Saxon potential parameter modifications（e.g.,the strength of the spin-orbit coupling and the nuclear surface diffuseness） on the fission barrier are briefly discussed.

Deconstructing Vibrational Motions on the Potential Energy Surfaces of Hydrogen-Bonded Complexes

Internal vibrations underlie transient structure formation,spectroscopy,and dynamics.However,at least two challenges exist when aiming to elucidate the contributions of vibrational motions on the potential energy surfaces.One is the acquisition of well-resolved experimental infrared spectra,and the other is the development of efficient theoretical methodologies that reliably predict band positions,relative intensities,and substructures.Here,we report size-specific infrared spectra of ammonia clusters to address these two challenges.Unprecedented agreement between experiment and state-of-the-art quantum simulations reveals that the vibrational spectra are mainly contributed by proton-donor ammonia.A striking Fermi resonance observed at approximately 3210 and 3250 cm^(−1)originates from the coupling of NH symmetric stretch fundamentals with overtones of free and hydrogen-bonded NH bending,respectively.These novel,intriguing findings contribute to a better understanding of vibrational motions in a large variety of hydrogen-bonded complexes with orders of magnitude improvements in spectral resolution,efficiency,and specificity.

A procedure of determining potential energy surfaces of triatomic molecules from inversion of spectroscopic data

In this paper, we have suggested an iterative procedure of optimization of the linear parameters in an analytic potential energy function for a triatomic molecule, by combining both variational and second order perturbation methods. The most important feature of this procedure is that the objective function is an analytical expression which can be optimized easily. The application to the water molecule is presented.

Differential diffusion quantum Monte Carlo method: determination of potential energy surfaces of molecules

A differential approach for self-optimizing diffusion Monte Carlo calculation was proposed in this paper, which is a new algorithm combining three techniques such as optimizing, diffusion and correlation sampling. This method can be used to directly compute the energy differential between two system in the diffusion process, making the statistical error of calculation be reduced to Order of 10?-5 hartree, and recover about more than 80% of the correlation. We employed this approach to set up a potential energy surface of a molecule, used a “rigid move” model, and utilized Jacobi transformation to make energy calculation for two configurations of a molecule having good positive correlation. So, an accurate energy differential could be obtained, and the potential energy surface with good quality can be depicted. In calculation, a technique called “post-equilibrium remaining sample” was set up firstly, which can save about 50% of computation expense. This novel algorithm was used to study the potential as molecular spectroscopy and the energy variation in chemical reactions.

Scattering Resonance States and Partial Potential Energy Surface of Reaction I+HI(v=0)→IH(v′=0) +I

The partial potential energy surface of the I ＋ HI →IH ＋ I reaction involving the translational and vibrational motions has been constructed at the QCISD（ T ）//MP4SDQ level with the pseudo potential method that is helpful to interpreting the scattering resonance states. The lifetimes of the scattering resonance states in the title reaction obtained from the partial potential energy surface are about 90-120 fs, which agrees with the result of high-resolved threshold photodetachment spectroscopy of anion IHI^- measured by Neumark.

Transport properties of a binary mixture of CO_2-N_2 from the pair potential energy functions based on a semi-empirical inversion method

The potential energy snrface of a CO2-N2 mixture is determined by using an inversion method, together with a new collision integral correlation [J. Phys. Chem. R@ Data 19 1179 （1990）]. With the new invert potential, the transport properties of CO2-N2 mixture are presented in a temperature range front 273.15 K to 3273.15 K at low density by employing the Chapman-Enskog scheme and the Wang Chang-Uhlenbeck de Boer theory, consisting of a viscosity coefficient, a thermal conductivity coefficient, a binary diffusion coefficient, and a thermal diffusion factor. The accuracy of the predicted results is estimated to be 2% for viscosity, 5% for thermal conductivity, and 10% for binary diffusion coefficient.

The effect of the attractive well of the potential energy surface for Ne-HC1 on rotationally inelastic partial wave cross sections

An interaction potential of the Ne-HC1 van der Waals complex is obtained by utilizing the Huxley analytic potential function to fit the accurate interaction energy data, which have been computed at the coupled cluster singles and doubles including connected triple excitations level and with the augmented correlation consistent polarized valence quintuple zeta basis set extended with a set of 3s3p2dlflg mid-bond functions [CCSD （T）/aug-cc-pV5Z-33211]. The close coupling calculation of state-to-state partial cross sections for collision of Ne with HC1 is first performed by employing the fitted interaction potential. This calculation is performed at the incident energies： 40, 60, 75 and 100 meV, separately. The effects of the long-range attractive and the short-range anisotropic interactions on the inelastic state-to-state partial cross sections are discussed in detail. Two maxima are present in the rotationally inelastic partial cross sections and they originate from different mechanisms.

Globally accurate ab initio based potential energy surface of H_2O^+(X^4A'')

A globally accurate potential energy surface is reported for the electronic ground-state H2O＋. The ab initio energies utilized to map the potential energy surface are calculated at the multireference configuration interaction method employing the aug-cc-pVQZ basis set and the full valence complete active space wave function as reference. In order to improve accu- racy of the resulting raw ab initio energies, they are then extrapolated to the complete basis set limit and most importantly to the full configuration-interaction limit by semiempirically correcting the dynamical correlation using the double many- body expansion-scaled external correlation method. The topographical features of the current potential energy surface were examined in detail, which agree nicely with those of other theoretical work.

Accurate double many-body expansion potential energy surface of HS_2(A^2A') by scaling the external correlation

A globally accurate single-sheeted double many-body expansion potential energy surface is reported for the first excited state of HS_2 by fitting the accurate ab initio energies, which are calculated at the multireference configuration interaction level with the aug-cc-pVQZ basis set. By using the double many-body expansion-scaled external correlation method,such calculated ab initio energies are then slightly corrected by scaling their dynamical correlation. A grid of 2767 ab initio energies is used in the least-square fitting procedure with the total root-mean square deviation being 1.406 kcal · mol^（-1）.The topographical features of the HS_2（A_2A＇） global potential energy surface are examined in detail. The attributes of the stationary points are presented and compared with the corresponding ab initio results as well as experimental and other theoretical data, showing good agreement. The resulting potential energy surface of HS_2（A_2A＇） can be used as a building block for constructing the global potential energy surfaces of larger S/H molecular systems and recommended for dynamic studies on the title molecular system.

A new global potential energy surface of the ground state of SiH_(2)^(+)(X^(2)A_(1))system and dynamics calculations of the Si^(+)+H_(2)(v_(0)=2,j_(0)=0)→SiH^(+)+H reaction

A global potential energy surface(PES)of the ground state of SiH_(2)^(+) system is built by using neural network method based on 18223 ab initio points.The topographic properties of PES are presented and compared with previous theoretical and experimental studies.The results indicate that the spectroscopic parameters obtained from the new PES are in good agreement with the experimental data.In order to further verify the validity of the new PES,a test dynamics calculation of the Si^(+)+H_(2)(v_(0)=2,j_(0)=0)→H+SiH^(+)reaction has been carried out by using the time-dependent wave packet method.The integral cross sections and rate constants are computed for the title reaction.The reasonable dynamical behavior indicates that the newly constructed PES is suitable for relevant dynamics investigations.

A full-dimensional analytical potential energy surface for the F+CH_4→HF+CH_3 reaction

A full-dimensional analytical potential energy surface （APES） for the F ＋ CH4 →HF ＋ CH3 reaction is developed based on 7127 ab initio energy points at the unrestricted coupled-cluster with single, double, and perturbative triple excitations. The correlation-consistent polarized triple-split valence basis set is used. The APES is represented with a many-body expansion containing 239 parameters determined by the least square fitting method. The two-body terms of the APES are fitted by potential energy curves with multi-reference configuration interaction, which can describe the diatomic molecules （CH, H2, HF, and CF） accurately. It is found that the APES can reproduce the geometry and vibrational frequencies of the saddle point better than those available in the literature. The rate constants based on the present APES support the experimental results of Moore et al. [Int. J. Chem. Kin. 26, 813 （1994）]. The analytical first-order derivation of energy is also provided, making the present APES convenient and efficient for investigating the title reaction with quasiclassical trajectory calculations.

Stereodynamics Study of Li+HF→LiF+H Reactions on X^2A’ Potential Energy Surface at Collision Energies below 5.00 kcal/mol

The product rotational polarizations of reaction Li-SHF→LiF-kH at different collision energies, as well as at the different vibrational states and rotational states, are calculated by using the quasi-classical trajectory method based on a new potential energy surface constructed by Aguado et al. [J. Chem. Phys. 119（2003） 10088]. We investigate the Mignment and the orientation of the product molecule by calculating the P（θr, φr） distribu- tions describing polar angle distribution, the P（θr） distributions describing the k-j＇ correlation and the P（φr） distributions describing the k-k＇-j＇ correlation. We also explore the dependence of reaction probabilities and cross sections on the rotational and vibrational quantum number of the title reaction. It is concluded that the vibrational state has more important impact on the angular distribution, reaction probability and cross section.

Theoretical Study of the Scattering Resonance State, Reaction Mechanism and Partial Potential Energy Surface of the F+CH4→HF+CH3 Reaction

The partial potential energy surface was constructed by ab initio method [QCISD（T）/6- 311＋＋G（2df,2pd）]for F＋CH4→HF＋CH3 reaction system. It not only explained the reaction mechanism brought forward by Diego Troya by means of quasiclassical trajectory （QCT） but also successfully validated Kopin Liu＇s experimental phenomena about the existence of the reactive resonance. The lifetime of the scattering resonance state was about 0.07 ps. All these were in agreement with the experiments.

Theoretical Studies on the Potential Energy Surface and Vibrational Energy Levels of HXeBr

The potential energy surface for the electronic ground state of the HXeBr molecule is constructed from more than 4200 ab initio points calculated using the internally contracted multi-reference configuration interaction method with the Davidson correction （icMRCI ＋ Q）. The stabilities and dissociation barriers are identified from the potential energy surface. The three-body dissociation channel is found to be the dominant dissociation channel for HXeBr. Low-lying vibrational energy levels of HXeBr calculated using the Lanczos algorithm are found to be in good agreement with the available experimental band origins.

AN AB INITIO SORBIE-MURREL POTENTIAL ENERGY SURFACE OF CARBON DISULFIDE

In this letter ab initio electronic structure calculations are performed for extensive geometries Of CS2. A newly written program is used to fit the computed energies into the Sorbie-Murrel function, whose contour plots are illustrated.

Surface available gravitational potential energy in the world oceans

Satellite altimetry observations,including the upcoming Surface Water and Ocean Topography mission,provide snapshots of the global sea surface high anomaly field.The common practice in analyzing these surface elevation data is to convert them into surface velocity based on the geostrophic approximation.With increasing horizontal resolution in satellite observations,sea surface elevation data will contain many dynamical signals other than the geostrophic velocity.A new physical quantity,the available surface potential energy,is conceptually introduced in this study defined as the density multiplied by half of the squared deviation from the local mean reference surface elevation.This gravitational potential energy is an intrinsic property of the sea surface height field and it is an important component of ocean circulation energetics,especially near the sea surface.In connection with other energetic terms,this new variable may help us better understand the dynamics of oceanic circulation,in particular the processes in connection with the free surface data collected through satellite altimetry.The preliminary application of this concept to the numerically generated monthly mean Global Ocean Data Assimilation System data and Archiving,Validation,and Interpretation of Satellite Oceanographic altimeter data shows that the available surface potential energy is potentially linked to other dynamic variables,such as the total kinetic energy,eddy kinetic energy and available potential energy.

Atomistic Modeling of Lithium Materials from Deep Learning Potential with Ab Initio Accuracy

Lithium has been paid great attention in recent years thanks to its significant appli-cations for battery and lightweight alloy.Developing a potential model with high ac-curacy and efficiency is impor-tant for theoretical simulation of lithium materials.Here,we build a deep learning potential(DP)for elemental lithium based on a concurrent-learning scheme and DP representation of the density-functional theory(DFT)potential energy surface(PES),the DP model enables material simulations with close-to DFT accuracy but at much lower computational cost.The simulations show that basic parameters,equation of states,elasticity,defects and surface are consistent with the first principles results.More notably,the liquid radial distribution func-tion based on our DP model is found to match well with experiment data.Our results demon-strate that the developed DP model can be used for the simulation of lithium materials.