title: π-Conjugation in trans-1,3-butadiene: static and dynamical electronic correlations described through quantum Monte Carlo.
abstract: We investigate the effects of the static and dynamical electronic correlations on the level of conjugation of the trans-1,3-butadiene molecule through Quantum Monte Carlo methods applied to an Antisymmetrized Geminal Power (AGP) wave function, with a Jastrow factor similar to the Gutzwiller ansatz. The degree of conjugation is measured through the convergence of the structural properties of 1,3-butadiene and in particular of the Bond Length Alternation (BLA), that is the difference between the lengths of the single and double carbon bonds. After verifying the different roles of the Fermionic AGP part of our wave function and of the Jastrow factor in recovering electronic correlation, we study the effects of a constrained Active Space AGP (AGPAS), similar to that used in the Complete Active Space (CAS) representation. Through this AGPAS, we are able to identify the effect of the limited active space on the degree of conjugation, showing that in the limit of infinite active space the structural properties converge exactly to those of the atomic AGP, giving a BLA for 1,3-butadiene around 0.1244(5) Å.
authors.affiliation: Dipartimento di Ingegneria e Scienze dell'Informazione e Matematica, Università degli studi dell'Aquila , L'Aquila, Italy.|Dipartimento di Scienze Fisiche e Chimiche, Università degli studi dell'Aquila , , L'Aquila, Italy.
authors.forename: Matteo
authors.initials: M
authors.lastname: Barborini
authors.affiliation: Dipartimento di Scienze Fisiche e Chimiche, Università degli studi dell'Aquila , , L'Aquila, Italy.
authors.forename: Leonardo
authors.initials: L
authors.lastname: Guidoni