The Effect of Indium Content on the Atomic Environment and Cluster Stability of GeSe4Inx=10,15 Glasses
Abstract
:1. Introduction
2. Methodology
Partial | GeSe4In10 | GeSe4In15 | ||
---|---|---|---|---|
rmin | rmax | rmin | rmax | |
Ge–Se | 2.00 | 2.95 | 1.95 | 2.95 |
Se–Se | 1.95 | 2.75 | 2.05 | 2.75 |
Se–In | 2.30 | 2.90 | 2.30 | 2.90 |
3. Results and Discussion
3.1. Pair Distribution Functions
Total | Ge-Ge | Se-Se | In-In | Ge-In | Se-In | |
---|---|---|---|---|---|---|
GeSe4In10 | 0.31 | 0.16 | 0.41 | 0.23 | 0.16 | 0.46 |
GeSe4In15 | 0.26 | 0.21 | 0.36 | 0.18 | 0.14 | 0.40 |
3.2. Atomic Environment Statistics and Cluster Selection
Reference system | Center atom | Cluster designation | Average coordination of cluster center | Cluster density (g/mL) | Cluster number density (Atoms/Å3) | Central atom distance from RMC box origin (Å) | Number of Ge surface atoms | Number of Se surface atoms | Number of In surface atoms |
---|---|---|---|---|---|---|---|---|---|
GeSe4In10 | Ge | 34 | 14 | 6.268 | 0.03(2859) | 2.865 | 0 | 2 | 12 |
GeSe4In10 | Se | 248 | 14 | 6.410 | 0.03(3600) | 3.037 | 1 | 1 | 12 |
GeSe4In10 | Se | 371 | 11 | 5.598 | 0.03(0197) | 2.734 | 1 | 2 | 8 |
GeSe4In10 | In | 1276 | 14 | 7.709 | 0.04(1329) | 1.256 | 1 | 3 | 10 |
GeSe4In10 | In | 2088 | 15 | 6.716 | 0.03(5206) | 4.513 | 1 | 2 | 12 |
GeSe4In15 | Ge | 61 | 16 | 6.995 | 0.03(8950) | 9.441 | 0 | 5 | 11 |
GeSe4In15 | Ge | 73 | 15 | 7.224 | 0.03(9512) | 23.148 | 0 | 4 | 11 |
GeSe4In15 | Ge | 109 | 15 | 7.053 | 0.03(6971) | 23.075 | 0 | 2 | 13 |
GeSe4In15 | Se | 479 | 12 | 6.779 | 0.03(4477) | 6.715 | 0 | 1 | 11 |
GeSe4In15 | Se | 564 | 14 | 6.765 | 0.03(4554) | 8.228 | 0 | 1 | 13 |
GeSe4In15 | Se | 668 | 11 | 7.518 | 0.03(7109) | 2.086 | 0 | 0 | 11 |
GeSe4In15 | Se | 671 | 14 | 7.713 | 0.04(1187) | 8.277 | 0 | 3 | 11 |
GeSe4In15 | Se | 713 | 13 | 5.878 | 0.03(0678) | 5.771 | 0 | 2 | 11 |
GeSe4In15 | In | 865 | 14 | 7.563 | 0.03(9488) | 6.124 | 0 | 3 | 11 |
GeSe4In15 | In | 1735 | 14 | 6.772 | 0.03(3854) | 5.810 | 0 | 1 | 13 |
GeSe4In15 | In | 2219 | 14 | 7.458 | 0.03(9824) | 5.467 | 0 | 4 | 10 |
GeSe4In15 | In | 2502 | 17 | 7.582 | 0.04(0358) | 6.267 | 0 | 4 | 13 |
3.3. Binding Energy Decomposition and Molecular Orbital Interactions
Cluster name | Spin polarization | Ne | Pauli (a.u.) | Electrostatic (a.u.) | Orbital Interactions (a.u.) |
---|---|---|---|---|---|
GeSe4In10-Se371 | 1 | 526 | 5.201 | −1.666 | −4.925 |
GeSe4In10-In1276 | 1 | 673 | 6.341 | −2.053 | −5.522 |
GeSe4In15-Ge61 | 1 | 741 | 6.011 | −1.966 | −5.379 |
GeSe4In10-Ge34 | 1 | 688 | 4.781 | −1.545 | −4.439 |
GeSe4In15-In2219 | 1 | 675 | 5.701 | −1.823 | −5.046 |
GeSe4In15-Ge73 | 1 | 707 | 6.151 | −2.035 | −5.304 |
GeSe4In15-Se671 | 1 | 675 | 5.269 | −1.721 | −4.671 |
GeSe4In15-Ge109 | 1 | 737 | 4.701 | −1.401 | −4.491 |
GeSe4In15-Se479 | 0 | 607 | 4.729 | −1.465 | −4.231 |
GeSe4In15-In2502 | 1 | 822 | 6.708 | −2.134 | −5.866 |
GeSe4In15-In865 | 0 | 690 | 5.335 | −1.673 | −4.737 |
GeSe4In15-Se564 | 1 | 705 | 5.040 | −1.528 | −4.586 |
GeSe4In15-Se668 | 0 | 573 | 3.983 | −1.207 | −3.626 |
GeSe4In15-Se713 | 1 | 641 | 5.860 | −1.955 | −4.839 |
GeSe4In10-In2088 | 0 | 737 | 6.065 | −1.924 | −5.166 |
GeSe4In15-In1735 | 0 | 720 | 5.094 | −1.535 | −4.551 |
GeSe4In10-Se248 | 1 | 688 | 4.032 | −1.301 | −3.576 |
4. Conclusions
- (1)
- The extra In content of the GeSe4In15 system appeared to have substantially demoted contributions from Ge–Se in favor of Se–In, which shaped the shell almost exclusively. The role of Se–Se was faint, in similarity to GeSe4In10.
- (2)
- In both glasses studied, interactions beyond the first coordination shell revealed great similarity among the shapes of the partials involved. The Se–In partial was instrumental towards second coordination shell formation; Ge–In contributed only fractionally towards second coordination and this behavior was common to both alloys. Third shell interatomic interactions comprised two overlapping peaks at 3.3 and 3.5 Å due to Se–In and In–In interactions.
- (3)
- The excess In content in GeSe4In15 mediated the formation of rich Ge-centered clusters at radial distances further than 4 Å from the RMC center, an effect which also flagged the reduction of bonding between Ge and Se near the RMC center.
- (4)
- Ge–Se and Se–In bonding promoted overall cluster stability and the intervention of excess In caused breaking of these bonds contributed towards a lower binding energy.
- (5)
- The introduction of excess In resulted in higher Se–In cooperation towards frontier orbitals. Direct interactions between Ge and In were scarce and limited to the GeSe4In10 glass. On the whole, Ge and Se competed for connectivity with Se over the whole range of valence electron energies; however, Indium, particularly in the GeSe4In15 system, was far more effective in bonding with Se.
Author Contributions
Conflicts of Interest
References
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Antipas, G.S.E.; Mangiorou, E.; Hristoforou, E. The Effect of Indium Content on the Atomic Environment and Cluster Stability of GeSe4Inx=10,15 Glasses. Metals 2015, 5, 102-118. https://doi.org/10.3390/met5010102
Antipas GSE, Mangiorou E, Hristoforou E. The Effect of Indium Content on the Atomic Environment and Cluster Stability of GeSe4Inx=10,15 Glasses. Metals. 2015; 5(1):102-118. https://doi.org/10.3390/met5010102
Chicago/Turabian StyleAntipas, Georgios S. E., Eleni Mangiorou, and Evangelos Hristoforou. 2015. "The Effect of Indium Content on the Atomic Environment and Cluster Stability of GeSe4Inx=10,15 Glasses" Metals 5, no. 1: 102-118. https://doi.org/10.3390/met5010102