6533b828fe1ef96bd12890a5

RESEARCH PRODUCT

Theoretical study of the low‐lying states of trans‐1,3‐butadiene

Luis Serrano-andrésIgnacio Nebot-gilJosé Sánchez-marín

subject

ButadieneElectronic correlationChemistryGeneral Physics and AstronomyMultireference configuration interactionPolyenesConfiguration interactionChromophoresUNESCO::FÍSICA::Química físicaConfiguration InteractionComputational chemistryAb initio quantum chemistry methodsExcited stateButadiene ; Ab Initio Calculations ; Configuration Interaction ; Perturbation Theory ; Energy Levels ; Molecular Orbital Method ; Polyenes ; Biology ; ChromophoresEnergy LevelsPerturbation TheoryPerturbation theory (quantum mechanics)Molecular Orbital MethodPhysical and Theoretical ChemistryAtomic physicsGround stateWave function:FÍSICA::Química física [UNESCO]Ab Initio CalculationsBiology

description

We present extensive ab initio calculations on the low‐lying electronic states of trans‐1,3‐butadiene within the multireference configuration interaction (MRCI) framework by selecting the configurations with a perturbative criterion. The X 1Ag ground state and 1 3Bu, 1 3Ag, 2 1Ag, and 1 1Bu valence excited states have been calculated at a fixed geometry. The results obtained are in good agreement with previous experimental and calculated values, and could help to understand polyene spectroscopy, photochemistry, and photophysics. The advantages of a MRCI method where the most important contributions to the total MRCI wave function, perturbatively selected, are treated variationally, and the remaining terms are evaluated by means of a perturbational approach, are also discussed. Furthermore, a criterion in order to build a correlation‐consistent configuration interaction space is stated and, therefore, a reliable approximation to achieve accurate energy differences is obtained. Several monoelectronic molecular‐orbital basis functions are tried in order to select the most adequate to describe each state. Luis.Serrano@uv.es ; Jose.Sanchez@uv.es ; Ignacio.Nebot@uv.es

yearjournalcountryeditionlanguage
1992-11-15
10.1063/1.463521http://hdl.handle.net/10550/12886