Beyond vibrational self-consistent-field methods: Benchmark calculations for the fundamental vibrations of ethylene

A number of different methods for calculation of vibrational energies are reviewed and tested for calculation of the fundamental vibrational frequencies for ethylene. The methods tested for the description of the vibrational states are vibrational self consistent field (VSCF), vibrational configurat...

Descripción completa

Detalles Bibliográficos
Autores: Christiansen, Ove, Luis Luis, Josep Maria
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2005
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/16569
Acceso en línea:http://hdl.handle.net/10256/16569
Access Level:acceso abierto
Palabra clave:Càlcul de variacions
Calculus of variations
Dinàmica molecular
Molecular dynamics
Espectres vibracionals
Vibrational spectra
Descripción
Sumario:A number of different methods for calculation of vibrational energies are reviewed and tested for calculation of the fundamental vibrational frequencies for ethylene. The methods tested for the description of the vibrational states are vibrational self consistent field (VSCF), vibrational configuration interaction (VCI), vibrational M{\o}ller-Plesset theory (VMP), and vibrational coupled cluster (VCC). The convergence of the different methods towards the full vibrational configuration interaction (FVCI) result is discussed for a modest-sized one-mode basis. For larger one-mode basis sets results are presented for selected methods. Different representations of the potential energy surface are compared including full and partial quartic force field as well as expansions using up to sixth derivatives of the potential energy surface. Using MP2 electronic structure theory the electronic structure basis set convergence is tested