Theoretical Prediction of the Structure of Insulating <span class="aps-inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><mrow><msub><mrow><mi>YH</mi></mrow><mrow><mn>3</mn></mrow></msub></mrow></math></span>

P. J. Kelly; J. P. Dekker; R. Stumpf

doi:10.1103/PhysRevLett.78.1315

Access by Xinjiang University

Theoretical Prediction of the Structure of Insulating ${YH}_{3}$

P. J. Kelly

J. P. Dekker

R. Stumpf

Philips Research Laboratories, Prof. Holstlaan 4, 5656 AA Eindhoven, The Netherlands

Faculty of Physics and Astronomy, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands

Sandia National Laboratories, Albuquerque, New Mexico 87185-1413

PDF

Phys. Rev. Lett. 78, 1315 – Published 17 February, 1997

DOI: https://doi.org/10.1103/PhysRevLett.78.1315

Abstract

Density functional calculations of the total energy have been used to determine minimum energy structures for ${YH}_{3}$ . Small, symmetry lowering displacements of the hydrogen atoms lead to a structure with an energy which is lower than that of any other structure considered so far and the opening of a large band gap sufficient to explain the recently observed metal-insulator transition in the ${YH}_{x}$ system.

Comments & Replies

Comment on “Theoretical Prediction of the Structure of Insulating Y $H_{3}$ ”

T. J. Udovic, Q. Huang, and J. J. Rush

Phys. Rev. Lett. 79, 2920 (1997)

Kelly, Dekker, and Stumpf Reply:

P. J. Kelly, J. P. Dekker, and R. Stumpf

Phys. Rev. Lett. 79, 2921 (1997)

References (24)

J. N. Huiberts, R. Griessen, H. H. Rector, R. J. Wijngaarden, J. P. Dekker, D. G. de Groot, and N. J. Koeman, Nature (London) 380, 231 (1996).
J. H. Weaver, R. Rosei, and D. T. Peterson, Phys. Rev. B 19, 4855 (1979) J. H. Weaver, D. T. Peterson, and R. L. Benbow, 20, 5301 (1979).
D. J. Peterman, B. N. Harmon, J. Marchiando, and J. H. Weaver, Phys. Rev. B 19, 4867 (1979).
J. N. Daou and P. Vajda, Phys. Rev. B 45, 10 907 (1992).
J. N. Huiberts, Ph.D. thesis, Vrije Universiteit Amsterdam, 1995.
J. P. Dekker, J. van Ek, A. Lodder, and J. N. Huiberts, J. Phys. Condens. Matter 5, 4805 (1993).
Y. Wang and M. Y. Chou, Phys. Rev. Lett. 71, 1226 (1993) Phys. Rev. B 51, 7500 (1995).
M. Mansmann and W. E. Wallace, J. Phys. (Paris) 25, 454 (1964).
N. F. Miron, V. I. Shcherbak, V. N. Bykov, and V. A. Levdik, Sov. Phys. Crystallogr. 17, 342 (1972).
T. J. Udovic, Q. Huang, and J. J. Rush, J. Phys. Chem. Solids 57, 423 (1996).
R. Eder and G. Sawatzky (unpublished); K. K. Ng, F. C. Zhang, V. I. Anisimov, and T. M. Rice (to be published).
R. Car and M. Parrinello, Phys. Rev. Lett. 55, 2471 (1985) R. Stumpf and M. Scheffler, Comput. Phys. Commun. 79, 447, Cat. No. ACTF (1994).
Near-perfect agreement with experiment is found for the band gaps of C, Si, Ge, and LiC by M. S. Hybertsen and S. G. Louie, Phys. Rev. Lett. 55, 1418 (1985) Phys. Rev. B 34, 5390 (1986) R. W. Godby, M. Schlüter, and L. J. Sham, Phys. Rev. Lett. 56, 2415 (1986) Phys. Rev. B 37, 10 159 (1988).
We used the parametrization of J. Perdew and A. Zunger, Phys. Rev. B 23, 5048 (1981).
N. Troullier and J. L. Martins, Phys. Rev. B 43, 1993 (1991).
L. Kleinman and D. M. Bylander, Phys. Rev. Lett. 48, 1425 (1982).
S. G. Louie, S. Froyen, and M. L. Cohen, Phys. Rev. B 26, 1738 (1982).
We used the first order ( $N = 1$ ) scheme of M. Methfessel and A. T. Paxton, Phys. Rev. B 40, 3616 (1989).
Y. Wang and M. Y. Chou, Phys. Rev. B 44, 10 339 (1991).
The irreducible representations are most conveniently determined using atom centered orbitals. To do this we carried out linearized muffin tin orbital calculations for the geometry determined by energy minimization in the plane wave pseudopotential scheme.
L. Hedin, Phys. Rev. 139, A796 (1965). $G$ is the exact “interacting” one-particle Green's function; $W$ is the screened Coulomb interaction $ε^{- 1} υ$ .
It is tempting to extend the analogy between ${YH}_{3}$ and Si to the heavier ${LaH}_{3}$ and Ge. For both of these materials the best LDA calculations result in vanishingly small band gaps. Self-energy corrections for Ge, calculated perturbatively, result in a band gap of 0.75 eV [[13]]. It is very probable that a similar approximation for ${LaH}_{3}$ will result in a comparably large gap. In order to make a detailed comparison with the absorption experiments of Ref. [[1]] optical matrix elements would have to be included.
M. Y. Chou and Y. Wang, in Proceedings of the International Symposium on Metal Hydrogen Systems, Les Diablerets, 1996, K. Yvon [J. Alloys Compd. (to be published)].
The 70 meV per unit cell energy difference between the insulating state and the metallic ${HoD}_{3}$ structure cannot be compared to $kT$ because it would cost much more than 70 meV to prepare a single unit cell in the ${HoD}_{3}$ structure if all the surrounding cells had the insulating structure. Since observation of metallic behavior requires having a large number of metallic unit cells, the free energies of the low symmetry insulating state and the higher symmetry metallic state need to be calculated—a nontrivial problem.

[c1] J. N. Huiberts, R. Griessen, H. H. Rector, R. J. Wijngaarden, J. P. Dekker, D. G. de Groot, and N. J. Koeman, Nature (London) 380, 231 (1996).

[c2] J. H. Weaver, R. Rosei, and D. T. Peterson, Phys. Rev. B 19, 4855 (1979) J. H. Weaver, D. T. Peterson, and R. L. Benbow, 20, 5301 (1979).

[c3] D. J. Peterman, B. N. Harmon, J. Marchiando, and J. H. Weaver, Phys. Rev. B 19, 4867 (1979).

[c4] J. N. Daou and P. Vajda, Phys. Rev. B 45, 10 907 (1992).

[c5] J. N. Huiberts, Ph.D. thesis, Vrije Universiteit Amsterdam, 1995.

[c6] J. P. Dekker, J. van Ek, A. Lodder, and J. N. Huiberts, J. Phys. Condens. Matter 5, 4805 (1993).

[c7] Y. Wang and M. Y. Chou, Phys. Rev. Lett. 71, 1226 (1993) Phys. Rev. B 51, 7500 (1995).

[c8] M. Mansmann and W. E. Wallace, J. Phys. (Paris) 25, 454 (1964).

[c9] N. F. Miron, V. I. Shcherbak, V. N. Bykov, and V. A. Levdik, Sov. Phys. Crystallogr. 17, 342 (1972).

[c10] T. J. Udovic, Q. Huang, and J. J. Rush, J. Phys. Chem. Solids 57, 423 (1996).

[c11] R. Eder and G. Sawatzky (unpublished); K. K. Ng, F. C. Zhang, V. I. Anisimov, and T. M. Rice (to be published).

[c12] R. Car and M. Parrinello, Phys. Rev. Lett. 55, 2471 (1985) R. Stumpf and M. Scheffler, Comput. Phys. Commun. 79, 447, Cat. No. ACTF (1994).

[c13] Near-perfect agreement with experiment is found for the band gaps of C, Si, Ge, and LiC by M. S. Hybertsen and S. G. Louie, Phys. Rev. Lett. 55, 1418 (1985) Phys. Rev. B 34, 5390 (1986) R. W. Godby, M. Schlüter, and L. J. Sham, Phys. Rev. Lett. 56, 2415 (1986) Phys. Rev. B 37, 10 159 (1988).

[c14] We used the parametrization of J. Perdew and A. Zunger, Phys. Rev. B 23, 5048 (1981).

[c15] N. Troullier and J. L. Martins, Phys. Rev. B 43, 1993 (1991).

[c16] L. Kleinman and D. M. Bylander, Phys. Rev. Lett. 48, 1425 (1982).

[c17] S. G. Louie, S. Froyen, and M. L. Cohen, Phys. Rev. B 26, 1738 (1982).

[c18] We used the first order ( $N = 1$ ) scheme of M. Methfessel and A. T. Paxton, Phys. Rev. B 40, 3616 (1989).

[c19] Y. Wang and M. Y. Chou, Phys. Rev. B 44, 10 339 (1991).

[c20] The irreducible representations are most conveniently determined using atom centered orbitals. To do this we carried out linearized muffin tin orbital calculations for the geometry determined by energy minimization in the plane wave pseudopotential scheme.

[c21] L. Hedin, Phys. Rev. 139, A796 (1965). $G$ is the exact “interacting” one-particle Green's function; $W$ is the screened Coulomb interaction $ε^{- 1} υ$ .

[c22] It is tempting to extend the analogy between ${YH}_{3}$ and Si to the heavier ${LaH}_{3}$ and Ge. For both of these materials the best LDA calculations result in vanishingly small band gaps. Self-energy corrections for Ge, calculated perturbatively, result in a band gap of 0.75 eV [[13]]. It is very probable that a similar approximation for ${LaH}_{3}$ will result in a comparably large gap. In order to make a detailed comparison with the absorption experiments of Ref. [[1]] optical matrix elements would have to be included.

[c23] M. Y. Chou and Y. Wang, in Proceedings of the International Symposium on Metal Hydrogen Systems, Les Diablerets, 1996, K. Yvon [J. Alloys Compd. (to be published)].

[c24] The 70 meV per unit cell energy difference between the insulating state and the metallic ${HoD}_{3}$ structure cannot be compared to $kT$ because it would cost much more than 70 meV to prepare a single unit cell in the ${HoD}_{3}$ structure if all the surrounding cells had the insulating structure. Since observation of metallic behavior requires having a large number of metallic unit cells, the free energies of the low symmetry insulating state and the higher symmetry metallic state need to be calculated—a nontrivial problem.

Physical Review Letters

Export citation

Export citation

Theoretical Prediction of the Structure of Insulating ${YH}_{3}$

Abstract

Comments & Replies

Comment on “Theoretical Prediction of the Structure of Insulating Y $H_{3}$ ”

Kelly, Dekker, and Stumpf Reply:

References (24)

Outline

Information

Filter

Filter

Article Lookup

Enter a citation

Theoretical Prediction of the Structure of Insulating YH3

Abstract

Comments & Replies

Comment on “Theoretical Prediction of the Structure of Insulating YH3”

Kelly, Dekker, and Stumpf Reply:

References (24)

Theoretical Prediction of the Structure of Insulating ${YH}_{3}$

Comment on “Theoretical Prediction of the Structure of Insulating Y $H_{3}$ ”