A new global reaction route map on the potential energy surface of H2CO with unrestricted level

Abstract The potential energy surface (PES) of H2CO has been revisited by the anharmonic downward distortion following algorithm, where an unrestricted ab initio method was employed during the automated exploration. Some structures previously reported on the PES of restricted theories were found to be open-shell species, and new local minima and first-order saddle points were discovered in high energy regions related to radical fragments which are important in high energy processes such as combustion.

[1]  S. K. Lee,et al.  The Roaming Atom: Straying from the Reaction Path in Formaldehyde Decomposition , 2004, Science.

[2]  Satoshi Maeda,et al.  Global reaction route mapping on potential energy surfaces of formaldehyde, formic acid, and their metal-substituted analogues. , 2006, The journal of physical chemistry. A.

[3]  S. Klippenstein,et al.  Ab initio methods for reactive potential surfaces. , 2007, Physical chemistry chemical physics : PCCP.

[4]  Henry F. Schaefer,et al.  The photodissociation of formaldehyde: Potential energy surface features , 1979 .

[5]  F. Jensen.  Introduction to Computational Chemistry , 1998 .

[6]  K. Fukui.  The path of chemical reactions - the IRC approach , 1981 .

[7]  K. Ohno,et al.  Microsolvation of hydrogen sulfide: exploration of H2S.(H2O)n and SH-.H3O+.(H2O)n-1 (n = 5-7) cluster structures on ab initio potential energy surfaces by the scaled hypersphere search method. , 2008, The journal of physical chemistry. A.

[8]  Satoshi Maeda,et al.  Global reaction route mapping on potential energy surfaces of C2H7+ and C3H9+ , 2007 .

[9]  Tom Ziegler,et al.  A combined density functional and intrinsic reaction coordinate study on the ground state energy surface of H2CO , 1993 .

[10]  Satoshi Maeda,et al.  Automated exploration of adsorption structures of an organic molecule on RuH2-BINAP by the ONIOM method and the scaled hypersphere search method. , 2007, The journal of physical chemistry. A.

[11]  Satoshi Maeda,et al.  Global investigation on the potential energy surface of CH3CN: application of the scaled hypersphere search method. , 2005, The journal of physical chemistry. A.

[12]  K. Hirao,et al.  Transition state barrier height for the reaction H2CO→H2+CO studied by multireference Mo/ller–Plesset perturbation theory , 1997 .

[13]  Henry F. Schaefer,et al.  The photodissociation of formaldehyde: A coupled cluster study including connected triple excitations of the transition state barrier height for H2CO→H2+CO , 1989 .

[14]  J. Troe.  Refined analysis of the thermal dissociation of formaldehyde. , 2007, Journal of Physical Chemistry A.

[15]  G. DiLabio,et al.  Structure and binding energies in van der Waals dimers: Comparison between density functional theory and correlated ab initio methods , 2006 .

[16]  Satoshi Maeda,et al.  Insight into global reaction mechanism of [C2, H4, O] system from ab initio calculations by the scaled hypersphere search method. , 2007, The journal of physical chemistry. A.

[17]  Satoshi Maeda,et al.  Structures of water octamers (H2O)8: exploration on ab initio potential energy surfaces by the scaled hypersphere search method. , 2007, The journal of physical chemistry. A.

[18]  Yi Luo,et al.  Quantum chemistry study of H+(H2O)8: a global search for its isomers by the scaled hypersphere search method, and its thermal behavior. , 2007, The journal of physical chemistry. A.

[19]  Frank Jensen,et al.  Gradient extremal bifurcation and turning points: An application to the H2CO potential energy surface , 1996 .

[20]  D. Heidrich,et al.  Searching for saddle points of potential energy surfaces by following a reduced gradient , 1998 .

[21]  Satoshi Maeda,et al.  A scaled hypersphere search method for the topography of reaction pathways on the potential energy surface , 2004 .

[22]  David Feller,et al.  Barrier for the H2CO --> H2+ CO reaction: A discrepancy between high-level electronic structure calculations and experiment , 2000 .

[23]  Satoshi Maeda,et al.  Global mapping of equilibrium and transition structures on potential energy surfaces by the scaled hypersphere search method: applications to ab initio surfaces of formaldehyde and propyne molecules. , 2005, The journal of physical chemistry. A.

[24]  D. Moebius.  Molecular cooperation in monolayer organizates , 1981 .

[25]  Satoshi Maeda,et al.  Global analysis of reaction pathways on the potential energy surface of cyanoacetylene by the scaled hypersphere search method , 2006 .