222
A. V. Pomogaeva and A. Y. Timoshkin
+191
TS5a
-99
+41
-192
-36
-277
-134
-380
-238
-473
-364
-542
0
5
1a
TS6a
6
7
TS7
8
TS8
9
TS9
10
TS10
TS11
+195
-82
11
+123
TS12
-190
12
+93
TS13
-290
13
TS1a
+168
2
+35
+181
TS2a
-3
3
TS3a
+138
-40
4
0
100
200
-400
-100
-200
-300
ΔG 0 , kJ mol -1
-500
Fig. 6.12 Gibbs energy (in kJ mol −1 ) reaction profiles for considered pathways. Monomolecular
pathway (green); bimolecular pathway for [MeAlNH] 6 formation (red); and bimolecular pathway
for [Me 9 Al 6 N 6 H 9 ] formation (blue). M06-2X/def2-TZVPP//B3LYP/def2-SVP level of theory
(thermal corrections and entropies are at B3LYP/def2-SVP level of theory). (From [133] Copyright
© 2014 by John Wiley Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.)
A potentially interesting subclass of Ga-N-based nanostructures is oligomeric
clusters composed of [HGaNH] 3 rings with the wurtzitic arrangement of the GaN backbone. The rod-shaped oligomers are energetically more favorable than
cage-like isomers or three-dimensional structures [21, 23, 24, 45, 146–148]. High
polarizability of the rod-shaped oligomers along with tunable band gap makes
them promising charge carriers under an external electric field or under strength.
Such oligomer compounds were theoretically predicted [53], and, soon, family of
[RGaNH] n (R= H, CH 3 , C 2 H 5 , C 4 H 9 , C 6 H 13 ) rod-like compounds was synthesized
in ammonia solution [119].
Possible pathways for adjusting the band gap in such compounds include
variations in size, shape, substituents, dopant effects, and terminal effects. In the
present review, we summarize results of comprehensive computational studies of
how different factors affect structural and electronic properties of Ga-N-based rodlike oligomers. Schematic view of the considered rod-like oligomers is shown in Fig.
6.13. The building block of oligomers is the chair-shaped [RGaNH] 3 ring, where R
is hydrogen atom or methyl group.
In the present chapter, we will summarize results of computational studies of
electronic properties of rod-like [RMNH] 3n clusters of group 13 metals M=Al, Ga,
A. V. Pomogaeva and A. Y. Timoshkin
+191
TS5a
-99
+41
-192
-36
-277
-134
-380
-238
-473
-364
-542
0
5
1a
TS6a
6
7
TS7
8
TS8
9
TS9
10
TS10
TS11
+195
-82
11
+123
TS12
-190
12
+93
TS13
-290
13
TS1a
+168
2
+35
+181
TS2a
-3
3
TS3a
+138
-40
4
0
100
200
-400
-100
-200
-300
ΔG 0 , kJ mol -1
-500
Fig. 6.12 Gibbs energy (in kJ mol −1 ) reaction profiles for considered pathways. Monomolecular
pathway (green); bimolecular pathway for [MeAlNH] 6 formation (red); and bimolecular pathway
for [Me 9 Al 6 N 6 H 9 ] formation (blue). M06-2X/def2-TZVPP//B3LYP/def2-SVP level of theory
(thermal corrections and entropies are at B3LYP/def2-SVP level of theory). (From [133] Copyright
© 2014 by John Wiley Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.)
A potentially interesting subclass of Ga-N-based nanostructures is oligomeric
clusters composed of [HGaNH] 3 rings with the wurtzitic arrangement of the GaN backbone. The rod-shaped oligomers are energetically more favorable than
cage-like isomers or three-dimensional structures [21, 23, 24, 45, 146–148]. High
polarizability of the rod-shaped oligomers along with tunable band gap makes
them promising charge carriers under an external electric field or under strength.
Such oligomer compounds were theoretically predicted [53], and, soon, family of
[RGaNH] n (R= H, CH 3 , C 2 H 5 , C 4 H 9 , C 6 H 13 ) rod-like compounds was synthesized
in ammonia solution [119].
Possible pathways for adjusting the band gap in such compounds include
variations in size, shape, substituents, dopant effects, and terminal effects. In the
present review, we summarize results of comprehensive computational studies of
how different factors affect structural and electronic properties of Ga-N-based rodlike oligomers. Schematic view of the considered rod-like oligomers is shown in Fig.
6.13. The building block of oligomers is the chair-shaped [RGaNH] 3 ring, where R
is hydrogen atom or methyl group.
In the present chapter, we will summarize results of computational studies of
electronic properties of rod-like [RMNH] 3n clusters of group 13 metals M=Al, Ga,