Supplementary Information
On the Way to the Highest Coordination Number in the Planar Metal-Centred Aromatic Ta©B10− Cluster: Evolution of the Structures of TaBn− (n = 3 – 8)
Wei-Li Li,1 Alexander S. Ivanov,2 Jozef Federič,3 Constantin Romanescu,1 Ivan Černušák,3, c)Alexander
I. Boldyrev2,b) and Lai-Sheng Wang1, a)
1
Department of Chemistry, Brown University, Providence, Rhode Island 02912, USA.
Department of Chemistry and Biochemistry, Utah State University, 0300 Old Main Hill, Logan, Utah 843220300, USA.
3
Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská
dolina CH1, 84215 Bratislava, Slovakia.
2
E-mails: a) Lai-Sheng_Wang@brown.edu; b) a.i.bldyrev@usu.edu; c) cernusak@fns.uniba.sk
Figure S1. Photoelectron Spectra of TaB3− at (a) 532 nm, (b) 355 nm, (c) 266 nm, and (d) 193 nm.
S2
Figure S2. Photoelectron Spectra of TaB4− at (a) 355 nm, (b) 266 nm, and (c) 193 nm.
S3
Figure S3. Photoelectron Spectra of TaB5− at (a) 355 nm, (b) 266 nm, and (c) 193 nm.
S4
Figure S4. Photoelectron Spectra of TaB6− at (a) 355 nm, (b) 266 nm, and (c) 193 nm.
S5
Figure S5. Photoelectron Spectra of TaB7− at (a) 355 nm, (b) 266 nm, and (c) 193 nm.
S6
Figure S6. Low-lying structures of TaB3−, their point group symmetries, spectroscopic states and ZPE
corrected relative energies. The energies are given at: CCSD(T)/Ta/Stuttgart/B/aug-cc-pVTZ (top),
CCSD(T)/Ta/Stuttgart/B/aug-cc-pVQZ (in brackets), PBE0/Ta/Stuttgart/B/aug-cc-pVTZ (square brackets), all at PBE0/Ta/Stuttgart/B/aug-cc-pVTZ optimized geometries.
S7
Figure S7. Low-lying structures of TaB4−, their point group symmetries, spectroscopic states and ZPE
corrected relative energies. The energies are given at: CCSD(T)/Ta/Stuttgart/B/aug-cc-pVTZ (top),
CCSD(T)/Ta/Stuttgart/B/aug-cc-pVQZ (in brackets), PBE0/Ta/Stuttgart/B/aug-cc-pVTZ (square brackets), all at PBE0/Ta/Stuttgart/B/aug-cc-pVTZ optimized geometries.
S8
Figure S8. Low-lying structures of TaB5−, their point group symmetries, spectroscopic states and ZPE
corrected relative energies. The energies are given at: CCSD(T)/Ta/Stuttgart/B/aug-cc-pVTZ (top),
CCSD(T)/Ta/Stuttgart/B/aug-cc-pVQZ (in brackets), PBE0/Ta/Stuttgart/B/aug-cc-pVTZ (square brackets), all at PBE0/Ta/Stuttgart/B/aug-cc-pVTZ optimized geometries.
S9
Figure S9. Low-lying structures of TaB6−, their point group symmetries, spectroscopic states and ZPE
corrected relative energies. The energies are given at: CCSD(T)/Ta/Stuttgart/B/aug-cc-pVTZ (top),
PBE0/Ta/Stuttgart/B/aug-cc-pVTZ (square brackets), all at PBE0/Ta/Stuttgart/B/aug-cc-pVTZ optimized geometries.
S10
Figure S10. Low-lying structures of TaB7−, their point group symmetries, spectroscopic states and ZPE
corrected relative energies. The energies are given at: CCSD(T)/Ta/Stuttgart/B/aug-cc-pVTZ (top),
PBE0/Ta/Stuttgart/B/aug-cc-pVTZ (square brackets), all at PBE0/Ta/Stuttgart/B/aug-cc-pVTZ optimized geometries.
S11
Figure S11. Low-lying structures of TaB8−, their point group symmetries, spectroscopic states and ZPE
corrected relative energies. The energies are given at: CCSD(T)/Ta/Stuttgart/B/aug-cc-pVTZ (top),
PBE0/Ta/Stuttgart/B/aug-cc-pVTZ (square brackets), all at PBE0/Ta/Stuttgart/B/aug-cc-pVTZ optimized geometries.
S12
Table S1. Calculated VDEs for the I.2 (C2v, 2A2), and I.3 (C2v, 4A2) low-lying isomers of TaB3−. All energies are
in eV.
VDE (theo)
Final State and electronic configuration
ROPBE1PBEa
ROCCSD(T)
b
I.2. C2v (2A2)
A2, {…2b2(2)1b1(2)3a1(2)4a1(1)1a2(1)}
1
A1, {…2b2(2)1b1(2)3a1(2)4a1(2)1a2(0)}
3B , {…2b (2)1b (1)3a (2)4a (2)1a (1)}
2
2
1
1
1
2
3
3
A2,
3
A1,
5
B1,
5A ,
2
5B ,
2
I.3. C2v (
{...1b2(2)1b1(2)3a1(2)2b2(2)4a1(1)5a1(0)5a2(1)}
{...1b2(2)1b1(2)3a1(2)2b2(2)4a1(1)5a1(1)5a2(0)}
{...1b2(2)1b1(2)3a1(2)2b2(1)4a1(1)5a1(1)5a2(1)}
{...1b2(2)1b1(2)3a1(1)2b2(2)4a1(1)5a1(1)5a2(1)}
{...1b2(2)1b1(1)3a1(2)2b2(2)4a1(1)5a1(1)5a2(1)}
c
2.19
c
1.64
2.09
4.26
4
A2)
c
1.86
2.76
2.51
3.52
1.60
1.70
2.68
2.82
3.70
aVDEs
were calculated at ROPBE1PBE/Ta/Stuttgart/B/aug-cc-pVTZ//PBE1PBE/Ta/Stuttgart/B/aug-cc-pVTZ.
were calculated at ROCCSD(T)/Ta/Stuttgart/B/aug-cc-pVTZ//PBE1PBE/Ta/Stuttgart/B/aug-cc-pVTZ.
cVDE could not be calculated at this level of theory.
bVDEs
S13
Table S2. Cartesian coordinates (PBE0/Ta/Stuttgart/B/aug-cc-pVTZ) for structures I.1, I.2, I.3, II.1,
II.2, III.1, III.2, IV.1, IV.2, IV.3, V.1, VI.1.
I.1
Ta
0.000000000
0.000000000
0.310617000
B
B
B
0.000000000
0.000000000
0.000000000
1.356723000
0.000000000
-1.356723000
-1.263631000
-2.007752000
-1.263631000
I.2
Ta
0.000000000
0.000000000
0.385215000
B
0.000000000
0.000000000
-2.702822000
B
0.000000000
0.956763000
-1.460655000
B
0.000000000
-0.956763000
-1.460655000
I.3
Ta
B
B
B
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.878612000
0.000000000
-0.878612000
0.393933000
-1.477612000
-2.796201000
-1.477612000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.791596000
1.797560000
-0.791596000
-1.797560000
0.343866000
-1.837713000
-0.672511000
-1.837713000
-0.672511000
II.2
Ta
0.123525000
B
-0.450865000
B
-0.450865000
-0.326757000
1.784179000
0.601149000
0.000000000
0.782341000
-1.774903000
II.1
Ta
B
B
B
B
S14
B
B
-0.450865000
-0.450865000
1.784179000
0.601149000
-0.782341000
1.774903000
S15
III.1
Ta
B
B
B
B
B
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
1.473708000
-2.049553000
2.049553000
0.000000000
-1.473708000
0.374833000
-1.565454000
-0.158866000
-0.158866000
-2.023922000
-1.565454000
III.2
Ta
B
B
B
B
B
-0.323171000
0.652068000
1.390218000
-0.861572000
1.747563000
1.790023000
-0.215555000 -0.036041000
1.921720000
0.050648000
-0.699016000
1.047369000
1.775231000
0.244697000
0.844925000 -0.312278000
-0.695762000 -0.504240000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
1.400741000
-1.400741000
1.532470000
0.000000000
0.000000000
-1.532470000
0.735137000
-2.336756000
-2.336756000
-0.760767000
-3.098672000
-1.439279000
-0.760767000
Ta
0.000000000
0.000000000
0.626308000
B
0.000000000
1.502568000
-0.935774000
B
-0.906860000
0.000000000
-1.192146000
B
0.000000000
0.800469000
-2.444131000
B
0.906860000
0.000000000
-1.192146000
B
0.000000000
-1.502568000
-0.935774000
B
0.000000000
-0.800469000
-2.444131000
IV.1
Ta
B
B
B
B
B
B
IV.2
S16
IV.3
Ta
B
B
B
B
B
B
0.000000000
0.000000000
0.946117000
0.000000000
0.946117000
-0.946117000
-0.946117000
0.000000000
1.815461000
0.791220000
-1.815461000
-0.791220000
-0.791220000
0.791220000
0.475720000
-0.632823000
-1.419968000
-0.632823000
-1.419968000
-1.419968000
-1.419968000
0.505414000
-0.319525000
-1.586818000
-0.319525000
-1.288293000
-1.288293000
-1.288293000
-1.288293000
0.013870000
-0.399830000
1.170835000
-0.399830000
-0.999721000
0.712881000
-0.999721000
0.712881000
0.000000000
1.962937000
0.000000000
-1.962937000
-0.792284000
1.470259000
0.792284000
-1.470259000
-0.000021000
0.777993000
1.886668000
1.886668000
0.777993000
-0.783584000
-1.880921000
-1.880921000
-0.783584000
0.375862000
-0.696246000
-0.682060000
-0.682060000
-0.696246000
-0.674200000
-0.691289000
-0.691289000
-0.674200000
0.000000000
1.885350000
0.773552000
-0.773552000
-1.885350000
-1.883774000
-0.787877000
0.787877000
1.883774000
V.1
Ta
B
B
B
B
B
B
B
VI.1
Ta
B
B
B
B
B
B
B
B
S17