New phases of 3d-transition metal-cerium binary compounds: An extensive structural search

Xiaorui Sun, Yawei Lei, Rulong Zhou, Bingyan Qu, Dongdong Li, Bo Zhang, Xiao Cheng Zeng

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

We perform a comprehensive study to explore the low-energy crystalline phases of 3d transitional metal-cerium (TM-Ce) binary compounds using an unbiased structural search method coupled with first-principles optimization. For Ce-Sc, Ce-Ti, Ce-V, Ce-Cr and Ce-Mn binary systems, no stable crystalline phases are found from the structural search, offering an explanation for why none of these binary compounds have been observed in experiments. For Ce-Fe, Ce-Co, Ce-Ni, Ce-Cu and Ce-Zn binary systems, in addition to the previously known experimental structures, we also find several new low-energy crystalline phases. The computed electronic structures show that Ce atoms are in different states in the predicted binary compounds. In the Ce-Fe, Ce-Co and Ce-Ni compounds, the Ce 4f electrons are partially itinerant so that Ce atoms tend to adopt intermediate valence states between Ce+4 and Ce+3 due to the hybridization among Ce-4f, Ce-5d states and 3d states of TM. In the Ce-Cu and Ce-Zn binary compounds, the Ce-4f states are more localized with the charge state of Ce being close to 3+. In particular, the ferromagnetic metal (FM)-rich phases of the Ce-Fe, Ce-Co and Ce-Ni compounds tend to exhibit FM ordering in their ground states, owing to the strong exchange interaction among metal elements, whereas the non-magnetic states are usually preferred for FM-deficient phases. Magnetic orderings are also found in some other TM-rich phases of Ce-Cu and Ce-Zn compounds, where the magnetic moments are located on the Ce atoms due to the Kondo effect. Mechanic properties of these compounds are also computed based on density functional theory methods. This systematic study offers significantly new data for Ce-based alloys and will be useful to understand the intriguing behavior of the Ce-4f electron, thereby calling for future experimental confirmation of the newly predicted phases of Ce-TM compounds.

Original languageEnglish (US)
Pages (from-to)40486-40498
Number of pages13
JournalRSC Advances
Volume7
Issue number64
DOIs
StatePublished - Jan 1 2017

Fingerprint

Cerium
Ferromagnetic materials
Transition metals
Crystalline materials
Atoms
Metals
Kondo effect
Electrons
Exchange interactions
Magnetic moments
Chemical elements
Ground state
Electronic structure
Density functional theory
Magnetization
Mechanics
Experiments

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

New phases of 3d-transition metal-cerium binary compounds : An extensive structural search. / Sun, Xiaorui; Lei, Yawei; Zhou, Rulong; Qu, Bingyan; Li, Dongdong; Zhang, Bo; Zeng, Xiao Cheng.

In: RSC Advances, Vol. 7, No. 64, 01.01.2017, p. 40486-40498.

Research output: Contribution to journalArticle

Sun, Xiaorui ; Lei, Yawei ; Zhou, Rulong ; Qu, Bingyan ; Li, Dongdong ; Zhang, Bo ; Zeng, Xiao Cheng. / New phases of 3d-transition metal-cerium binary compounds : An extensive structural search. In: RSC Advances. 2017 ; Vol. 7, No. 64. pp. 40486-40498.
@article{67a597bf93454bb18ae9d838b6e84476,
title = "New phases of 3d-transition metal-cerium binary compounds: An extensive structural search",
abstract = "We perform a comprehensive study to explore the low-energy crystalline phases of 3d transitional metal-cerium (TM-Ce) binary compounds using an unbiased structural search method coupled with first-principles optimization. For Ce-Sc, Ce-Ti, Ce-V, Ce-Cr and Ce-Mn binary systems, no stable crystalline phases are found from the structural search, offering an explanation for why none of these binary compounds have been observed in experiments. For Ce-Fe, Ce-Co, Ce-Ni, Ce-Cu and Ce-Zn binary systems, in addition to the previously known experimental structures, we also find several new low-energy crystalline phases. The computed electronic structures show that Ce atoms are in different states in the predicted binary compounds. In the Ce-Fe, Ce-Co and Ce-Ni compounds, the Ce 4f electrons are partially itinerant so that Ce atoms tend to adopt intermediate valence states between Ce+4 and Ce+3 due to the hybridization among Ce-4f, Ce-5d states and 3d states of TM. In the Ce-Cu and Ce-Zn binary compounds, the Ce-4f states are more localized with the charge state of Ce being close to 3+. In particular, the ferromagnetic metal (FM)-rich phases of the Ce-Fe, Ce-Co and Ce-Ni compounds tend to exhibit FM ordering in their ground states, owing to the strong exchange interaction among metal elements, whereas the non-magnetic states are usually preferred for FM-deficient phases. Magnetic orderings are also found in some other TM-rich phases of Ce-Cu and Ce-Zn compounds, where the magnetic moments are located on the Ce atoms due to the Kondo effect. Mechanic properties of these compounds are also computed based on density functional theory methods. This systematic study offers significantly new data for Ce-based alloys and will be useful to understand the intriguing behavior of the Ce-4f electron, thereby calling for future experimental confirmation of the newly predicted phases of Ce-TM compounds.",
author = "Xiaorui Sun and Yawei Lei and Rulong Zhou and Bingyan Qu and Dongdong Li and Bo Zhang and Zeng, {Xiao Cheng}",
year = "2017",
month = "1",
day = "1",
doi = "10.1039/c7ra07103e",
language = "English (US)",
volume = "7",
pages = "40486--40498",
journal = "RSC Advances",
issn = "2046-2069",
publisher = "Royal Society of Chemistry",
number = "64",

}

TY - JOUR

T1 - New phases of 3d-transition metal-cerium binary compounds

T2 - An extensive structural search

AU - Sun, Xiaorui

AU - Lei, Yawei

AU - Zhou, Rulong

AU - Qu, Bingyan

AU - Li, Dongdong

AU - Zhang, Bo

AU - Zeng, Xiao Cheng

PY - 2017/1/1

Y1 - 2017/1/1

N2 - We perform a comprehensive study to explore the low-energy crystalline phases of 3d transitional metal-cerium (TM-Ce) binary compounds using an unbiased structural search method coupled with first-principles optimization. For Ce-Sc, Ce-Ti, Ce-V, Ce-Cr and Ce-Mn binary systems, no stable crystalline phases are found from the structural search, offering an explanation for why none of these binary compounds have been observed in experiments. For Ce-Fe, Ce-Co, Ce-Ni, Ce-Cu and Ce-Zn binary systems, in addition to the previously known experimental structures, we also find several new low-energy crystalline phases. The computed electronic structures show that Ce atoms are in different states in the predicted binary compounds. In the Ce-Fe, Ce-Co and Ce-Ni compounds, the Ce 4f electrons are partially itinerant so that Ce atoms tend to adopt intermediate valence states between Ce+4 and Ce+3 due to the hybridization among Ce-4f, Ce-5d states and 3d states of TM. In the Ce-Cu and Ce-Zn binary compounds, the Ce-4f states are more localized with the charge state of Ce being close to 3+. In particular, the ferromagnetic metal (FM)-rich phases of the Ce-Fe, Ce-Co and Ce-Ni compounds tend to exhibit FM ordering in their ground states, owing to the strong exchange interaction among metal elements, whereas the non-magnetic states are usually preferred for FM-deficient phases. Magnetic orderings are also found in some other TM-rich phases of Ce-Cu and Ce-Zn compounds, where the magnetic moments are located on the Ce atoms due to the Kondo effect. Mechanic properties of these compounds are also computed based on density functional theory methods. This systematic study offers significantly new data for Ce-based alloys and will be useful to understand the intriguing behavior of the Ce-4f electron, thereby calling for future experimental confirmation of the newly predicted phases of Ce-TM compounds.

AB - We perform a comprehensive study to explore the low-energy crystalline phases of 3d transitional metal-cerium (TM-Ce) binary compounds using an unbiased structural search method coupled with first-principles optimization. For Ce-Sc, Ce-Ti, Ce-V, Ce-Cr and Ce-Mn binary systems, no stable crystalline phases are found from the structural search, offering an explanation for why none of these binary compounds have been observed in experiments. For Ce-Fe, Ce-Co, Ce-Ni, Ce-Cu and Ce-Zn binary systems, in addition to the previously known experimental structures, we also find several new low-energy crystalline phases. The computed electronic structures show that Ce atoms are in different states in the predicted binary compounds. In the Ce-Fe, Ce-Co and Ce-Ni compounds, the Ce 4f electrons are partially itinerant so that Ce atoms tend to adopt intermediate valence states between Ce+4 and Ce+3 due to the hybridization among Ce-4f, Ce-5d states and 3d states of TM. In the Ce-Cu and Ce-Zn binary compounds, the Ce-4f states are more localized with the charge state of Ce being close to 3+. In particular, the ferromagnetic metal (FM)-rich phases of the Ce-Fe, Ce-Co and Ce-Ni compounds tend to exhibit FM ordering in their ground states, owing to the strong exchange interaction among metal elements, whereas the non-magnetic states are usually preferred for FM-deficient phases. Magnetic orderings are also found in some other TM-rich phases of Ce-Cu and Ce-Zn compounds, where the magnetic moments are located on the Ce atoms due to the Kondo effect. Mechanic properties of these compounds are also computed based on density functional theory methods. This systematic study offers significantly new data for Ce-based alloys and will be useful to understand the intriguing behavior of the Ce-4f electron, thereby calling for future experimental confirmation of the newly predicted phases of Ce-TM compounds.

UR - http://www.scopus.com/inward/record.url?scp=85028009692&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85028009692&partnerID=8YFLogxK

U2 - 10.1039/c7ra07103e

DO - 10.1039/c7ra07103e

M3 - Article

AN - SCOPUS:85028009692

VL - 7

SP - 40486

EP - 40498

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 64

ER -