Validation of convolution approximation to the thermal-average electron density

Autor:	Tibor Koritsanszky, J. Robert Michael
Rok vydání:	2014
Předmět:	Quantum chemical Electron density Chemistry Applied Mathematics Gaussian Mathematics::Rings and Algebras Basis function Probability density function General Chemistry Physics::Geophysics Convolution Vibration symbols.namesake Quantum mechanics Thermal symbols Statistical physics
Zdroj:	Journal of Mathematical Chemistry. 53:250-259
ISSN:	1572-8897 0259-9791
DOI:	10.1007/s10910-014-0425-y
Popis:	Analytic evaluation of the dynamic (thermally smeared) molecular electron density (ED) is described within the LCAO-MO and harmonic-convolution approximations. The key step is to assign vibration probability density functions (PDFs) to the two-center products of Gaussian basis functions used in quantum chemical models, if the PDFs of the nuclear centers are known. Based on internal modes of vibrations of small molecules it is demonstrated how the convoluted ED relates to the stationary (static) ED, as well as to that of the average over an ensemble of static EDs calculated for near-equilibrium nuclear geometries using clamped Hamiltonians. The overall effect of neglecting correlated nuclear motions on the convoluted ED is also illuminated.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::39c27518a2ca9a54e4ac7d7b7e90d0cf https://doi.org/10.1007/s10910-014-0425-y Zobrazit plný text záznamu Full text from SpringerLink