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Updated: May 2, 2026

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Published on: October 10, 2016
Electron correlation in benzene: A QMC study of neutral and charged states
Edson Rodrigues de Oliveira1, Renato Pessoa1, Ladir Cândido1
1Instituto de Física, Universidade Federal de Goiás - UFG, 74001-970 Goiânia, GO, Brazil.
Abstract:
In this paper, we employ variational Monte Carlo and fixed-node diffusion Monte Carlo (FN-DMC) methods to investigate electron correlation effects in neutral and charged benzene molecules. Using orbitals from Hartree-Fock (HF) and density functional theory calculations, FN-DMC with the frozen-core approximation yields correlation energies consistent with CCSD(T) and ph-AFQMC, while all-electron FN-DMC lowers the correlation energy by ∼0.27 a.u., highlighting the role of core-electron contributions. On average, all-electron FN-DMC predicts vertical [VIP: 0.3477(34) a.u.] and adiabatic [AIP: 0.3433(39) a.u.] ionization potentials, both slightly above the experimental value [0.339 70(2) a.u.]. Zero-point vibrational energy (ZPVE) corrections adjust the VIP and AIP by -0.012 and +0.0037 a.u., respectively, improving agreement with experiment. Compared to HF, FN-DMC incorporates an additional 0.055 a.u. (≈1.5 eV) of correlation energy into the IP, demonstrating its effectiveness in capturing electron correlation in aromatic systems.
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