A global ab initio potential energy surface for the X 2A′ ground state of the Si + OH → SiO + H reaction

Dayou, Fabrice; Duflot, Denis; Rivero-Santamaría, Alejandro; Monnerville, Maurice
November 2013
Journal of Chemical Physics;Nov2013, Vol. 139 Issue 20, p204305
Academic Journal
We report the first global potential energy surface (PES) for the X 2A′ ground electronic state of the Si(3P) + OH(X2Π) → SiO(X1Σg+) + H(2S) reaction. The PES is based on a large number of ab initio energies obtained from multireference configuration interaction calculations plus Davidson correction (MRCI+Q) using basis sets of quadruple zeta quality. Corrections were applied to the ab initio energies in the reactant channel allowing a proper description of long-range interactions between Si(3P) and OH(X2Π). An analytical representation of the global PES has been developed by means of the reproducing kernel Hilbert space method. The reaction is found barrierless. Two minima, corresponding to the SiOH and HSiO isomers, and six saddle points, among which the isomerization transition state, have been characterized on the PES. The vibrational spectra of the SiOH/HSiO radicals have been computed from second-order perturbation theory and quantum dynamics methods. The structural, energetic, and spectroscopic properties of the two isomers are in good agreement with experimental data and previous high quality calculations.


Related Articles

  • Quantum Computational Semantics on Fock Space. Chiara, M.; Giuntini, R.; Gudder, S.; Leporini, R. // International Journal of Theoretical Physics;Dec2005, Vol. 44 Issue 12, p2219 

    In the Fock space semantics, meanings of sentences are identified with density operators of the (unsymmetrized) Fock space $${\cal F}$$ based on the Hilbert space â„‚2. Generally, the meaning of a sentence is smeared over different sectors of $${\cal F}$$ . The standard quantum...

  • Basis sets in correlated effective potential calculations. Christiansen, P. A.; Christiansen, P.A. // Journal of Chemical Physics;6/15/2000, Vol. 112 Issue 23 

    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...

  • Microsolvation of CH in helium: An ab initio study. Solimannejad, Mohammad; Mirhoseini, Behnia Sadat; Esrafili, Mehdi D. // Journal of Theoretical & Computational Chemistry;Mar2016, Vol. 15 Issue 2, p-1 

    In the present study, microsolvation and interaction of the CH cation with He clusters are investigated by means of ab initio calculations at MP2/aug-cc-pVTZ and QCISD/aug-cc-pVTZ levels. Stabilization energies of the studied complexes including basis set superposition error (BSSE) and zero...

  • Full-dimensional ab initio potential energy surface and vibrational configuration interaction calculations for vinyl. Sharma, Amit R.; Braams, Bastiaan J.; Carter, Stuart; Shepler, Benjamin C.; Bowman, Joel M. // Journal of Chemical Physics;5/7/2009, Vol. 130 Issue 17, p174301 

    The potential energy landscape and two permutationally invariant, full-dimensional ab initio-based potential energy surfaces (PESs) for the doublet vinyl radical, C2H3, are described. The first of the two surfaces, denoted as PES/S, describes the equivalent CH2CH global minimum and the saddle...

  • H4+: What do we know about it? Alijah, Alexander; Varandas, António J. C. // Journal of Chemical Physics;7/21/2008, Vol. 129 Issue 3, p034303 

    The potential energy surface of H4+ has been analyzed and stationary points and minima of intersections characterized by benchmark multireference configuration interaction calculations with basis sets as large as augmented septuble zeta. No evidence for minima other than those of the well...

  • Third-order multireference perturbation theory: The n-electron valence state perturbation-theory approach. Angeli, Celestino; Bories, Benoît; Cavallini, Alex; Cimiraglia, Renzo // Journal of Chemical Physics;2/7/2006, Vol. 124 Issue 5, p054108 

    A formulation of the n-electron valence state perturbation theory (NEVPT) at the third order of perturbation is presented. The present implementation concerns the so-called strongly contracted variant of NEVPT, where only a subspace of the first-order interacting space is taken into account. The...

  • Ab initio electron propagator calculations in molecular transport junctions: Predictions of negative differential resistance. Kletsov, Aleksey; Dahnovsky, Yuri // Journal of Chemical Physics;10/14/2007, Vol. 127 Issue 14, p144716 

    In this work we study current-voltage characteristics in transport molecular junctions with a 1,4-benzene dithiol molecule as a bridge by using different ab initio electron propagator methods such as OVGF and P3 which are both programs in a Gaussian software package. The current-voltage...

  • Multiresolution potential energy surfaces for vibrational state calculations. Yagi, Kiyoshi; Hirata, So; Hirao, Kimihiko // Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Sep2007, Vol. 118 Issue 3, p681 

    A compact and robust many-mode expansion of potential energy surfaces (PES) is presented for anharmonic vibrations of polyatomic molecules, where the individual many-mode terms are approximated with various different resolutions, i.e., electronic structure methods, basis sets, and functional...

  • Vibrational and rotational cooling of NO+ in collisions with He. Stoecklin, T.; Voronin, A. // Journal of Chemical Physics;5/31/2011, Vol. 134 Issue 20, p204312 

    A quantum mechanical investigation of the vibrational and rotational deactivation of NO+ in collisions with He atoms in the cold and ultracold regime is presented. Ab initio potential energy calculations are carried out at BCCD(T) level and a new global 3D potential energy surface (PES) is...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics