%0 Journal Article %1 sutcliffe:22A544 %A Sutcliffe, Brian T. %A Woolley, R. Guy %D 2012 %I AIP %J The Journal of Chemical Physics %K chemistry energy mechanics physics potential quantum state surface theory transition %N 22 %P 22A544 %R 10.1063/1.4755287 %T On the quantum theory of molecules %U http://link.aip.org/link/?JCP/137/22A544/1 %V 137 %X Transition state theory was introduced in 1930s to account for chemical reactions. Central to this theory is the idea of a potential energy surface (PES). It was assumed that such a surface could be constructed using eigensolutions of the Schrödinger equation for the molecular (Coulomb) Hamiltonian but at that time such calculations were not possible. Nowadays quantum mechanical ab initio electronic structure calculations are routine and from their results PESs can be constructed which are believed to approximate those assumed derivable from the eigensolutions. It is argued here that this belief is unfounded. It is suggested that the potential energy surface construction is more appropriately regarded as a legitimate and effective modification of quantum mechanics for chemical purposes.

@article{sutcliffe:22A544, abstract = {Transition state theory was introduced in 1930s to account for chemical reactions. Central to this theory is the idea of a potential energy surface (PES). It was assumed that such a surface could be constructed using eigensolutions of the Schrödinger equation for the molecular (Coulomb) Hamiltonian but at that time such calculations were not possible. Nowadays quantum mechanical ab initio electronic structure calculations are routine and from their results PESs can be constructed which are believed to approximate those assumed derivable from the eigensolutions. It is argued here that this belief is unfounded. It is suggested that the potential energy surface construction is more appropriately regarded as a legitimate and effective modification of quantum mechanics for chemical purposes. }, added-at = {2013-01-18T05:21:29.000+0100}, author = {Sutcliffe, Brian T. and Woolley, R. Guy}, biburl = {https://www.bibsonomy.org/bibtex/29fe5a562987a9aa3dc32fc42af0ea504/drmatusek}, doi = {10.1063/1.4755287}, eid = {22A544}, interhash = {83a7c676454649ab72d7c9c41060b17f}, intrahash = {9fe5a562987a9aa3dc32fc42af0ea504}, journal = {The Journal of Chemical Physics}, keywords = {chemistry energy mechanics physics potential quantum state surface theory transition}, month = dec, number = 22, numpages = {8}, pages = {22A544}, publisher = {AIP}, timestamp = {2013-06-02T16:24:55.000+0200}, title = {On the quantum theory of molecules}, url = {http://link.aip.org/link/?JCP/137/22A544/1}, volume = 137, year = 2012 }