In search of the next Holy Grail of polyoxide chemistry: Explicitly correlated ab initio full quartic force fields for HOOH, HOOOH, HOOOOH, and their isotopologues

2012 ◽  
Vol 136 (8) ◽  
pp. 084302 ◽  
Author(s):  
David S. Hollman ◽  
Henry F. Schaefer
Keyword(s):  
Ab Initio ◽  
Force Fields ◽  
Holy Grail ◽  
Explicitly Correlated

scholarly journals High-level ab initio quartic force fields and spectroscopic characterization of C2N−

2021 ◽  
Author(s):  
Carlos M. Rocha ◽  
H V J Linnartz
Keyword(s):  
Ab Initio ◽  
Force Fields ◽  
Electron Attachment ◽  
Spectroscopic Characterization ◽  
Carbon Chain ◽  
Molecular Anions ◽  
High Level

While it is now well established that large carbon chain species and radiative electron attachment (REA) are key ingredients triggering interstellar anion chemistry, the role played by smaller molecular anions,...

Empirical Potential-Energy Surfaces Fitting Using Feed forward Neural Networks

2012 ◽  
Author(s):  
Lionel Raff ◽  
Ranga Komanduri ◽  
Martin Hagan ◽  
Satish Bukkapatnam
Keyword(s):  
Potential Energy ◽  
Ab Initio ◽  
Potential Energy Surfaces ◽  
Force Fields ◽  
Pair Potential ◽  
Potential Surfaces ◽  
Empirical Potential ◽  
Functional Forms ◽  
Dynamics Simulations ◽  
Energy Surfaces

When the system of interest becomes too complex to permit the use of ab initio methods to obtain the system potential-energy surfaces (PES), empirical potential surfaces are frequently employed to represent the force fields present in the system under investigation. In most cases, the functional forms present in these potentials are selected on the basis of chemical and physical intuitions. The parameters of the surface are frequently adjusted to fit a very small set of experimental data that comprise bond energies, equilibrium bond distances and angles, fundamental vibrational frequencies, and perhaps measured barrier heights to reactions of interest. Such potentials generally yield only qualitative or semiquantitative descriptions of the system dynamics. Several research groups have significantly improved the accuracy of the values of the experimental properties computed using empirical potential surfaces by fitting the chosen functional form for the potential to the force fields obtained from trajectories using ab initio Car-Parrinello molecular dynamics simulations. The fitting to the force fields is usually done using a least-squares fitting approach. This method has been employed by Izvekov et al. to obtain effective non-polarizable three-site force fields for liquid water. Carré et al. have employed such a procedure to obtain a new pair potential for silica. In their investigation, the vector of potential parameters was fitted using an iterative Levenberg-Marquardt algorithm. Tangney and Scandolo have also developed an interatomic force field for liquid SiO2 in which the parameters were fitted to the forces, stresses, and energies obtained from ab initio calculations. Ercolessi and Adams have used a quasi-Newtonian procedure to fit an empirical potential for aluminum to data obtained from first-principals computations. Empirical potentials can be improved by making the parameters parameterized functions of the coordinates defining the instantaneous positions of the atoms of the system. This approach has been successfully employed by numerous investigators The difficulty with this procedure is that the number of parameters that must be adjusted increases rapidly. Appropriate fitting of these parameters requires a much more extensive database. Finally, the actual fitting process can often be tedious, difficult, and time-consuming.

The Future

1992 ◽  
Author(s):  
John A. Tossell ◽  
David J. Vaughan
Keyword(s):  
Ab Initio ◽  
Quantum Chemical ◽  
Force Fields ◽  
Structural Characteristics ◽  
Future Research ◽  
Quantum Mechanical ◽  
Bond Lengths ◽  
Hartree Fock ◽  
Qualitative Level ◽  
Dynamics Simulations

In this final chapter, an attempt is made to provide an overview of the capabilities of quantum-mechanical methods at the present time, and to highlight the needs for future development and possible future applications of these methods, particularly in areas related to mineral structures, energetics, and spectroscopy. There is also a brief account of some new areas of application, specific directions for future research, and possible developments in the perception and use of quantum-mechanical approaches. The book ends with an epilog on the overall role of “theoretical geochemistry” in the earth and environmental sciences. The local structural characteristics of minerals such as Mg2SiO4, which contain only main-group elements, are reasonably well reproduced by ab initio Hartree-Fock-Roothaan (SCF) cluster calculations at the mediumbasis- set level. Calculations incorporating configuration interaction will inevitably follow and probably lead to somewhat better agreement with experiment. The most pressing needs in this area of study are for the development of systematic procedures for cluster selection and embedding, for a greater understanding of the results at a qualitative level, and for more widespread efficient application of the quantum-chemical results currently available. In the last area, substantial progress has already been made by Lasaga and Gibbs (1987), Sanders et al. (1984), Tsuneyuki et al. (1988), and others, who have used ab initio calculations to generate theoretical force fields which can then be used in molecular-dynamics simulations. If the characteristics of the resultant force fields can be understood at a first-principles level, then it may be possible to understand details of the simulated structures at the same level. Unfortunately, as regards a greater qualitative understanding of the quantum-mechanical calculations, little progress has been made. Rather old qualitative theories describe some aspects of bond-angle variation (Tossell, 1986), but no general model to interpret variations in bond lengths has been developed within either chemistry or geochemistry beyond the model of additive atomic (Slater) or ionic (Shannon and Prewitt) radii. Indeed, global theories of bond-length variations within an ab initio framework seem to be nonexistent. Nonetheless, quantum-chemical studies have shown the presence of intriguing systematics in bond lengths (Gibbs et al., 1987), which had been already noted empirically.

scholarly journals Rethinking the X− + CH3Y [X = OH, SH, CN, NH2, PH2; Y = F, Cl, Br, I] SN2 reactions

2019 ◽  
Vol 21 (15) ◽  
pp. 7924-7931 ◽  
Author(s):  
Domonkos A. Tasi ◽  
Zita Fábián ◽  
Gábor Czakó
Keyword(s):  
Ab Initio ◽  
Sn2 Reactions ◽  
Explicitly Correlated ◽  
Leaving Groups

Explicitly-correlated ab initio computations reveal novel inversion and retention pathways for several SN2 reactions with different nucleophiles and leaving groups.

scholarly journals Toward a W4-F12 approach: Can explicitly correlated and orbital-based ab initio CCSD(T) limits be reconciled?

2016 ◽  
Vol 144 (21) ◽  
pp. 214101 ◽  
Author(s):  
Nitai Sylvetsky ◽  
Kirk A. Peterson ◽  
Amir Karton ◽  
Jan M. L. Martin
Keyword(s):  
Ab Initio ◽  
Explicitly Correlated

Transformation of ab initio force fields in calculations of molecular vibrations using regundand vibrational coordinates

2011 ◽  
Vol 78 (5) ◽  
pp. 617-623 ◽  
Author(s):  
G. A. Pitsevich ◽  
A. V. Kostopravova ◽  
D. S. Umreiko ◽  
M. A. Ksenofontov
Keyword(s):  
Ab Initio ◽  
Force Fields ◽  
Molecular Vibrations
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