title: Which Density Functional Should Be Used to Describe Protonated Water Clusters?
abstract: Protonated water cluster is one of the most important hydrogen-bond network systems. Finding an appropriate DFT method to study the properties of protonated water clusters can substantially improve the economy in computational resources without sacrificing the accuracy compared to high-level methods. Using high-level MP2 and CCSD(T) methods as well as experimental results as benchmark, we systematically examined the effect of seven exchange-correlation GGA functionals (with BLYP, B3LYP, X3LYP, PBE0, PBE1W, M05-2X, and B97-D parametrizations) in describing the geometric parameters, interaction energies, dipole moments, and vibrational properties of protonated water clusters H+(H2O)2-9,12. The overall performance of all these functionals is acceptable, and each of them has its advantage in certain aspects. X3LYP is the best to describe the interaction energies, and PBE0 and M05-2X are also recommended to investigate interaction energies. PBE0 gives the best anharmonic frequencies, followed by PBE1W, B97-D and BLYP methods. PBE1W, B3LYP, B97-D, and X3LYP can yield better geometries. The capability of B97-D to distinguish the relative energies between isomers is the best among all the seven methods, followed by M05-2X and PBE0.
authors.affiliation: Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Dalian University of Technology, Ministry of Education , Dalian, 116024, China.
authors.forename: Ruili
authors.initials: R
authors.lastname: Shi
authors.affiliation: School of Ocean Science and Technology, Dalian University of Technology , Panjin Campus, Panjin, 124221, China.
authors.forename: Xiaoming
authors.initials: X
authors.lastname: Huang
authors.affiliation: Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Dalian University of Technology, Ministry of Education , Dalian, 116024, China.
authors.forename: Yan
authors.identifier: http://orcid.org/0000-0001-5669-9015
authors.initials: Y
authors.lastname: Su
authors.affiliation: Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Institute of Molecular Science, Shanxi University , Taiyuan, 030006, China.
authors.forename: Hai-Gang
authors.initials: HG
authors.lastname: Lu
authors.affiliation: Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Institute of Molecular Science, Shanxi University , Taiyuan, 030006, China.
authors.forename: Si-Dian
authors.initials: SD
authors.lastname: Li
authors.affiliation: College of Science, Dalian Nationalities University , Dalian 116600, China.
authors.forename: Lingli
authors.initials: L
authors.lastname: Tang
authors.affiliation: Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Dalian University of Technology, Ministry of Education , Dalian, 116024, China.
authors.forename: Jijun
authors.identifier: http://orcid.org/0000-0002-3263-7159
authors.initials: J
authors.lastname: Zhao