One‐body energy decomposition schemes revisited: Assessment of Mulliken‐, Grid‐, and conventional energy density analyses

The stability of the lithium ion battery (LIB) using LiCoO 2 as a cathode material in charging/discharging process was investigated on the basis of the first-principles density functional theory calculations. The voltage curve obtained by total electronic energy reproduced the trend of the experimental data such as the instability of the battery at the charged state. Mulliken's population analysis (MPA) and energy density analysis (EDA) techniques were utilized to estimate the partial charge and partial energy in Li x CoO 2 species. During charging/discharging, Mulliken charge of oxygen changes and, therefore, its local energy varies. On the other hand, the local energy of cobalt drastically changes at low lithium content, whereas its Mulliken charge approximately remains constant. The present results indicate that the local analysis is essential to clarify the origin of the stability of LIB.The stabilization and/or destabilization of lithium ion battery (LIB) in the operating process are of great interest from the practical and scientific points of view. The α-NaFeO 2 layered-type LiCoO 2 is widely utilized in commercial LIB as a cathode material. Following the discovery that LiMO 2 compounds (where M is a transition metal) exhibit an electrochemical potential of 4-5 V with respect to metallic lithium, LiCoO 2 has found extensive use in rechargeable batteries owing to its facile chemical synthesis and electrochemical stability during charge/discharge cycles. 1-4 The theoretical capacity of LiCoO 2 is 274 mAhg −1 ; nevertheless, only about 140 mAhg −1 of the capacity is harnessed in practical cells. The compositional range of Li x CoO 2 must be maintained between 0.5 ≤ x ≤ 1 to achieve good cycling stability. 5,6 Outside this range, structural phase transition occurs and the cycling stability is lost. Thus, the transformation from the layeredtype Li x CoO 2 to other types for x ≤ 0.5 has been intensively studied both experimentally 7-10 and theoretically. 11-15 For example, the formation of the spinel-type Li x CoO 2 was observed on the surfaces of the layered-type crystal after the long-term charge/discharge cycling. 9 Theoretical studies have supported that the spinel structure should be more stable than the layered one in the range of x ≤ 0.5. It was proposed that the migration of Co atoms caused the phase transition. 15 However, the origin of the cathode instability at low Li content still remains an open question.We focus on the local information of electronic structure and electronic energy in order to analyze the stability/instability of LiCoO 2 . The standard Mulliken's population analysis (MPA) 16,17 technique was used for the local charge variation. MPA is a simple approach for estimating partial atomic charges on the basis of linear combination of atomic orbitals. The energy density analysis (EDA) developed by Nakai 18-20 was adopted for the local energy change. Many researches using EDA succeeded in the evaluation of surface adsorption 21,22 and the design of novel organic materials 23 and inorganic m...

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“…[18][19][20] The EDA calculations were carried out with the use of extensional EDA code for PBC calculation developed by Nakai et al 28…”

Section: Methodsmentioning

confidence: 99%

Theoretical Study on Stability of Lithium Ion Battery in Charging Process: Analysis Based on Partial Charge and Partial Energy

Yamauchi

Nakai

2013

J. Electrochem. Soc.

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“…7, the trace operations run over all atomic orbitals (AOs), {µ}, assigned to atom K. In the case of KS-DFT, the xc energy may be treated in a similar manner, again partitioning the total density matrix solely on the basis of which atoms the individual AOs are localized on (that is, irrespective of any further population measure). 162 In contrast to EDA, the present partitioning in Eqs. 6 fundamentally operates on an MO rather than an AO level, which among other features offers tunability as we may employ different localization procedures and ways of defining the atom-RDM1s (cf.…”

Section: Atomic Partitioningsmentioning

confidence: 98%

Mean-Field Density Matrix Decompositions

Eriksen

2020

Preprint

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We introduce new and robust decompositions of mean-field Hartree-Fock (HF) and Kohn-Sham density functional theory (KS-DFT) relying on the use of localized molecular orbitals and physically sound charge population protocols. The new lossless property decompositions, which allow for partitioning 1-electron reduced density matrices into either bond-wise or atomic contributions, are compared to alternatives from the literature with regards to both molecular energies and dipole moments. Besides commenting on possible applications as an interpretative tool in the rationalization of certain electronic phenomena, we demonstrate how decomposed mean-field theory makes it possible to expose and amplify compositional features in the context of machinelearned quantum chemistry. This is made possible by improving upon the granularity of the underlying data. On the basis of our preliminary proof-of-concept results, we conjecture that many of the structure-property inferences in existence today may be further refined by efficiently leveraging an increase in dataset complexity and richness.

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“…Our group has developed analyzing methodologies based on the information of atomic orbitals (AOs) for total energy, which is the key quantity for quantum chemistry . This type of energy decomposition for ab initio methods such as Hartree–Fock in analogy to Mulliken‐type population analysis has a long history, and been proposed even now by several groups .…”

Section: Introductionmentioning

confidence: 99%

Kinetic energy decomposition scheme based on information theory

2013

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We proposed a novel kinetic energy decomposition analysis based on information theory. Since the Hirshfeld partitioning for electron densities can be formulated in terms of Kullback-Leibler information deficiency in information theory, a similar partitioning for kinetic energy densities was newly proposed. The numerical assessments confirm that the current kinetic energy decomposition scheme provides reasonable chemical pictures for ionic and covalent molecules, and can also estimate atomic energies using a correction with viral ratios.

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One‐body energy decomposition schemes revisited: Assessment of Mulliken‐, Grid‐, and conventional energy density analyses

Cited by 17 publications

References 56 publications

Theoretical Study on Stability of Lithium Ion Battery in Charging Process: Analysis Based on Partial Charge and Partial Energy

Theoretical Study on Stability of Lithium Ion Battery in Charging Process: Analysis Based on Partial Charge and Partial Energy

Mean-Field Density Matrix Decompositions

Kinetic energy decomposition scheme based on information theory

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