Rules and mechanisms governing octahedral tilts in perovskites under pressure

Rules and mechanisms governing octahedral tilts in perovskites under pressure The rotation of octahedra (octahedral tilting) is common in ABO3 perovskites and relevant to many physical phenomena, ranging from electronic and magnetic properties, metal-insulator transitions to improper ferroelectricity. Hydrostatic pressure is an efficient way to tune and control octahedral tiltings. However, the pressure behavior of such tiltings can dramatically differ from one material to another, with the origins of such differences remaining controversial. In this paper, we discover several new mechanisms and formulate a set of simple rules that allow us to understand how pressure affects oxygen octahedral tiltings via the use and analysis of first-principles results for a variety of compounds. Besides the known A-O interactions, we reveal that the interactions between specific B ions and oxygen ions contribute to the tilting instability. We explain the previously reported trend that the derivative of the oxygen octahedral tilting with respect to pressure (dR/dP) usually decreases with both the tolerance factor and the ionization state of the A ion by illustrating the key role of A-O interactions and their change under pressure. Furthermore, three new mechanisms/rules are discovered, namely that (i) the octahedral rotations in ABO3 perovskites with empty low-lying d states on the B site are greatly enhanced by pressure, in order to lower the electronic kinetic energy; (ii) dR/dP is enhanced when the system possesses weak tilt instabilities, and (iii) for the most common phase exhibited by perovskites—the orthorhombic Pbnm state—the in-phase and antiphase octahedral rotations are not automatically both suppressed or both enhanced by the application of pressure because of a trilinear coupling between these two rotation types and an antipolar mode involving the A ions. We further predict that the polarization associated with the so-called hybrid improper ferroelectricity could be manipulated by hydrostatic pressure by indirectly controlling the amplitude of octahedral rotations. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Physical Review B American Physical Society (APS)

Rules and mechanisms governing octahedral tilts in perovskites under pressure

Preview Only

Rules and mechanisms governing octahedral tilts in perovskites under pressure

Abstract

The rotation of octahedra (octahedral tilting) is common in ABO3 perovskites and relevant to many physical phenomena, ranging from electronic and magnetic properties, metal-insulator transitions to improper ferroelectricity. Hydrostatic pressure is an efficient way to tune and control octahedral tiltings. However, the pressure behavior of such tiltings can dramatically differ from one material to another, with the origins of such differences remaining controversial. In this paper, we discover several new mechanisms and formulate a set of simple rules that allow us to understand how pressure affects oxygen octahedral tiltings via the use and analysis of first-principles results for a variety of compounds. Besides the known A-O interactions, we reveal that the interactions between specific B ions and oxygen ions contribute to the tilting instability. We explain the previously reported trend that the derivative of the oxygen octahedral tilting with respect to pressure (dR/dP) usually decreases with both the tolerance factor and the ionization state of the A ion by illustrating the key role of A-O interactions and their change under pressure. Furthermore, three new mechanisms/rules are discovered, namely that (i) the octahedral rotations in ABO3 perovskites with empty low-lying d states on the B site are greatly enhanced by pressure, in order to lower the electronic kinetic energy; (ii) dR/dP is enhanced when the system possesses weak tilt instabilities, and (iii) for the most common phase exhibited by perovskites—the orthorhombic Pbnm state—the in-phase and antiphase octahedral rotations are not automatically both suppressed or both enhanced by the application of pressure because of a trilinear coupling between these two rotation types and an antipolar mode involving the A ions. We further predict that the polarization associated with the so-called hybrid improper ferroelectricity could be manipulated by hydrostatic pressure by indirectly controlling the amplitude of octahedral rotations.
Loading next page...
 
/lp/aps_physical/rules-and-mechanisms-governing-octahedral-tilts-in-perovskites-under-8CLJAQ08XU
Publisher
The American Physical Society
Copyright
Copyright © ©2017 American Physical Society
ISSN
1098-0121
eISSN
1550-235X
D.O.I.
10.1103/PhysRevB.96.054102
Publisher site
See Article on Publisher Site

Abstract

The rotation of octahedra (octahedral tilting) is common in ABO3 perovskites and relevant to many physical phenomena, ranging from electronic and magnetic properties, metal-insulator transitions to improper ferroelectricity. Hydrostatic pressure is an efficient way to tune and control octahedral tiltings. However, the pressure behavior of such tiltings can dramatically differ from one material to another, with the origins of such differences remaining controversial. In this paper, we discover several new mechanisms and formulate a set of simple rules that allow us to understand how pressure affects oxygen octahedral tiltings via the use and analysis of first-principles results for a variety of compounds. Besides the known A-O interactions, we reveal that the interactions between specific B ions and oxygen ions contribute to the tilting instability. We explain the previously reported trend that the derivative of the oxygen octahedral tilting with respect to pressure (dR/dP) usually decreases with both the tolerance factor and the ionization state of the A ion by illustrating the key role of A-O interactions and their change under pressure. Furthermore, three new mechanisms/rules are discovered, namely that (i) the octahedral rotations in ABO3 perovskites with empty low-lying d states on the B site are greatly enhanced by pressure, in order to lower the electronic kinetic energy; (ii) dR/dP is enhanced when the system possesses weak tilt instabilities, and (iii) for the most common phase exhibited by perovskites—the orthorhombic Pbnm state—the in-phase and antiphase octahedral rotations are not automatically both suppressed or both enhanced by the application of pressure because of a trilinear coupling between these two rotation types and an antipolar mode involving the A ions. We further predict that the polarization associated with the so-called hybrid improper ferroelectricity could be manipulated by hydrostatic pressure by indirectly controlling the amplitude of octahedral rotations.

Journal

Physical Review BAmerican Physical Society (APS)

Published: Aug 2, 2017

There are no references for this article.

Sorry, we don’t have permission to share this article on DeepDyve,
but here are related articles that you can start reading right now:

Explore the DeepDyve Library

Unlimited reading

Read as many articles as you need. Full articles with original layout, charts and figures. Read online, from anywhere.

Stay up to date

Keep up with your field with Personalized Recommendations and Follow Journals to get automatic updates.

Organize your research

It’s easy to organize your research with our built-in tools.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

Monthly Plan

  • Read unlimited articles
  • Personalized recommendations
  • No expiration
  • Print 20 pages per month
  • 20% off on PDF purchases
  • Organize your research
  • Get updates on your journals and topic searches

$49/month

Start Free Trial

14-day Free Trial

Best Deal — 39% off

Annual Plan

  • All the features of the Professional Plan, but for 39% off!
  • Billed annually
  • No expiration
  • For the normal price of 10 articles elsewhere, you get one full year of unlimited access to articles.

$588

$360/year

billed annually
Start Free Trial

14-day Free Trial