A semiclassical study of cis-trans isomerization in HONO using an interpolating moving least-squares potential

Pham, Phong; Guo, Yin
April 2013
Journal of Chemical Physics;Apr2013, Vol. 138 Issue 14, p144304
Academic Journal
The interpolating moving least-squares (IMLS) approach for constructing potential energy surfaces has been developed and employed in standard classical trajectory simulations in the past few years. We extend the approach to the tunneling regime by combining the IMLS fitting method and the semiclassical scheme that incorporates tunneling into classical trajectory calculations. Dynamics of cis-trans isomerization in nitrous acid (HONO) is studied as a test case to investigate various aspects of the approach such as the strategy for growing the surface, the basis set employed, the scaling of the IMLS fits, and the accuracy of the surface required for obtaining converged rate coefficients. The validity of the approach is demonstrated through comparison with other semiclassical and quantum mechanical studies on HONO.


Related Articles

  • A theoretical study of cis–trans isomerization in HONO using an empirical valence bond potential. Guo, Yin; Thompson, Donald L. // Journal of Chemical Physics;1/22/2003, Vol. 118 Issue 4, p1673 

    The empirical valence bond (EVB) approach proposed by Chang and Miller [J. Phys. Chem. 94, 5884 (1990)] for constructing global potential energy surfaces has the potential for treating large molecular systems. In this work, we slightly modify the expression of Chang and Miller by adding a...

  • Multidimensional tunneling dynamics on HSiOH cis-trans isomerization with... Taketsugu, Tetsuya; Watanabe, Naomitsu; Hirao, Kimihiko // Journal of Chemical Physics;8/22/1999, Vol. 111 Issue 8, p3410 

    Studies the multidimensional tunneling dynamics on cis-trans isomerization with interpolated potential energy surfaces. Generation of the ab initio potential energy surface for the cis-trans isomerization by the modified Sphepard interpolation method at the computational level of the complete...

  • Large-amplitude dynamics in vinyl radical: The role of quantum tunneling as an isomerization mechanism. Sharma, Amit R.; Bowman, Joel M.; Nesbitt, David J. // Journal of Chemical Physics;1/21/2012, Vol. 136 Issue 3, p034305 

    We report tunneling splittings associated with the large amplitude 1,2 H-atom migration to the global minima in the vinyl radical. These are obtained using a recent full-dimensional ab initio potential energy surface (PES) [A. R. Sharma, B. J. Braams, S. Carter, B. C. Shepler, and J. M. Bowman,...

  • The GeOH+–HGeO+ system: A detailed quantum mechanical study. Yamaguchi, Yukio; Richards, Claude A.; Schaefer, Henry F. // Journal of Chemical Physics;11/8/1995, Vol. 103 Issue 18, p7975 

    The ground state potential energy hypersurface of the GeOH+–HGeO+ system has been investigated employing ab initio electronic structure theory. First, geometries of two equilibrium and isomerization (1,2 hydrogen shift) reaction transition state were determined at the...

  • Normal mode and isomerization bending states in HCP: Periodic orbit assignment and spectroscopic signature. Farantos, Stavros C.; Keller, Hans-Martin; Schinke, Reinhard; Yamashita, Koichi; Morokuma, Keiji // Journal of Chemical Physics;6/22/1996, Vol. 104 Issue 24, p10055 

    We present exact quantum mechanical bound-state calculations for HCP using an ab initio potential energy surface. The main result is the existence of two distinct families of bending states: one with normal-mode-type behavior and wave functions confined to small bending angles and the other one...

  • Conformational analysis of 2-methyl-1,3,2-oxaza- and 2-methyl-1,3,2-oxathiaborinane associates with water molecule. Kuznetsov, V. // Russian Journal of Organic Chemistry;Sep2011, Vol. 47 Issue 9, p1380 

    The structure and conformational behavior of 1: 1 molecular assotsiates of 2-methyl-1,3,2-oxazaand 2-methyl-1,3,2-oxathiaborinanes with water were studied ab initio in terms of HF/6-31G( d) and PBE/3z quantum-chemical approximations. The most stable complexes are formed via hydrogen bonding with...

  • A classical trajectory study of the intramolecular dynamics, isomerization, and unimolecular dissociation of HO2. Perry, Jamin W.; Dawes, Richard; Wagner, Albert F.; Thompson, Donald L. // Journal of Chemical Physics;Aug2013, Vol. 139 Issue 8, p084319 

    The classical dynamics and rates of isomerization and dissociation of HO2 have been studied using two potential energy surfaces (PESs) based on interpolative fittings of ab initio data: An interpolative moving least-squares (IMLS) surface [A. Li, D. Xie, R. Dawes, A. W. Jasper, J. Ma, and H....

  • Time-dependent wave packet study on trans-cis isomerization of HONO driven by an external field. Richter, Falk; Gatti, Fabien; Léonard, Céline; Le Quéré, Frédéric; Meyer, Hans-Dieter // Journal of Chemical Physics;10/28/2007, Vol. 127 Issue 16, p164315 

    The present paper is devoted to a full quantum mechanical study of the cis→trans isomerization of HONO. In contrast to our previous study [Richter et al., J. Chem. Phys. 120, 6072 (2004)], the dynamics is now performed in the presence of an external time-dependent field in order to be...

  • Interpolating moving least-squares methods for fitting potential energy surfaces: Using classical trajectories to explore configuration space. Dawes, Richard; Passalacqua, Alessio; Wagner, Albert F.; Sewell, Thomas D.; Minkoff, Michael; Thompson, Donald L. // Journal of Chemical Physics;4/14/2009, Vol. 130 Issue 14, p144107 

    We develop two approaches for growing a fitted potential energy surface (PES) by the interpolating moving least-squares (IMLS) technique using classical trajectories. We illustrate both approaches by calculating nitrous acid (HONO) cis→trans isomerization trajectories under the control of...


Read the Article


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

Try another library?
Sign out of this library

Other Topics