1. Tamás Vörös, György Tarczay
Matrix Isolation and Computational Study of [2C, 2N, X] (X = S, Se) Isomers
Tamás Vörös, György Tarczay
Institute of Chemistry, Eötvös University
Budapest, Hungary

2. Outline of the presentation
Introduction, goals of our studies
Computational results
Experimental results
Summary

3. Outline of the presentation
Introduction, goals of our studies
Computational results
Experimental results
Summary

4. Introduction
Early 19th century: Wöhler: Ag-cyanate (AgOCN) Liebig: Ag-fulminate (AgCNO)
Isomerism
(Berzelius)
Presently:

5. Introduction
Sgr B2:
HNCO
HOCN
HNCS
HSCN
TCM-1:
HCNO

6. Introduction [1] AgCN + SCl2 NCSCN + 2 AgCl [2] AgNCSe + I2
NCSeSeCN + 2 AgI
NCSeCN + (NCSe)2Se
[1a] C. J. Burchell, P. Kilian, A. M. Z. Slawin, J. D. Woolins; Inorg. Chem., 45 (2006)
[1b] Z. Kisiel et al.; J. Phys. Chem. A, 117 (2013)
[2] F. Cataldo, Polyhedron, 19 (2000)

7. Goals of our studies To study the [2C, 2N, X] (X = S, Se) isomers
using quantum-chemical methods to compute: - equilibrium structures, relative energies - harmonic and anharmonic wavenumbers, IR intensities and UV excitation energies
using matrix-isolation technique to: - supplement the condensed-phase IR spectra of NCXCN - generate and spectroscopically identify new isomers from the NCXCN isomer

8. Outline of the presentation
Introduction, goals of our studies
Computational results
Experimental results
Summary

9. Equilibrium structuresa, relative energiesb
a CCSD(T)/aug-cc-pVTZ
b ΔE (CCSD(T)/aug-cc-pVTZ) + ΔZPVE (CCSD(T)/aug-cc-pVTZ)

10. Equilibrium structures
NCCNO
CNCNS
NCNCSe
MP2/6-31G* [3]
bent, quasilinear
bent
linear
CCSD(T)/ aug-cc-pVTZ
[3] M. Feher, T. Pasinszki, T. Veszpremi, Inorg. Chem., 34 (1995)

11. IR wavenumbers and intensitiesa – [2C, 2N, S]
NCNCS
NCSCN
NCCNS
NCSNC
NCC(NS)
2247 (459)
2181 (0.3)
2229 (719)
2161 (0.7)
2238 (12)
2013 (1229)
2171 (0.1)
2085 (274)
2033 (217)
1705 (1)
1177 (17)
650 (2)
1073 (100)
679 (11)
961 (50)
658 (3)
649 (7)
558 (32)
630b (20)
631 (4)
470 (40)
487 (1)
377 (0.005)
457b (3)
513 (4)
447 (3)
359 (0)
372 (15)
358 (2)
506 (0.1)
442 (10)
349 (4)
77 (10)
242 (0.01)
363 (10)
423 (7)
309 (2)
239 (2)
220 (15)
84 (4)
120 (8)
110 (6)
164 (6)
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharm. contributions
b) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/cc-pVDZ anharm. contributions
(IR intensities: harmonic CCSD(T)/aug-ccpVTZ)

12. IR wavenumbers and intensities – [2C, 2N, S]
CNNCSa
CNCNSb
CNSNCa
CNC(NS)a
2097 (4)
2291 (418)
2032 (86)
2084 (419)
1891 (1040)
2010 (302)
2003 (371)
1698 (10)
1094 (21)
1108 (147)
693 (23)
1038 (107)
719 (18)
564 (36)
685 (47)
668 (7)
522 (42)
349 (6)
414 (7)
486 (14)
418 (0.2)
266 (0.002)
255 (0.00)
479 (6)
308 (9)
70 (11)
244 (0.06)
327 (2)
273 (1)
195 (0.08)
170 (5)
111 (3)
105 (4)
143 (3)
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharm. contributions
b) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers
(IR intensities: harmonic CCSD(T)/aug-ccpVTZ)

13. IR wavenumbers and intensitiesa – [2C, 2N, Se]
NCNCSe
NCSeCN
NCCNSe
NCSeNC
NCC(NSe)
2257 (617)
2176 (2)
2222 (817)
2160 (2)
2233 (10)
2012 (1232)
2168 (1)
2088 (340)
2039 (241)
1702 (4)
1106 (16)
547 (6)
1003 (65)
551 (17)
930 (48)
510 (3)
528 (6)
406 (29)
533 (14)
587 (14)
434 (28)
439 (1)
393 (0.02)
406 (2)
501 (0.01)
429 (8)
330 (0.0)
352 (21)
325 (2)
434 (1)
404 (17)
316 (3)
94 (9)
220 (0.004)
350 (12)
387 (0.3)
282 (1)
215 (2)
217 (14)
65 (5)
104 (7)
97 (5)
142 (5)
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharm. contributions
b) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/cc-pVDZ anharm. contributions
(IR intensities: harmonic CCSD(T)/aug-ccpVTZ)

14. IR wavenumbers and intensitiesa – [2C, 2N, Se]
CNNCSe
CNCNSe
CNSeNC
CNC(NSe)
2109 (7)
2226 (461)
2040 (120)
2092 (426)
1859 (1032)
1972 (305)
2017 (396)
1702 (6)
1023 (30)
1033 (109)
565 (17)
1002 (113)
619 (42)
369 (30)
549 (43)
605 (24)
444 (36)
334 (15)
346 (6)
457 (4)
380 (0.02)
275 (0.5)
229 (0.0)
420 (8)
299 (9)
96 (8)
219 (0.05)
303 (2)
270 (1)
179 (0.05)
172 (5)
99 (4)
94 (4)
132 (2)
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharm. contributions
(IR intensities: harmonic CCSD(T)/aug-ccpVTZ)

15. Outline of the presentation
Introduction, goals of our studies
Computational results
Experimental results
Summary

16. Preparation of NCSCN 2 AgCN + SCl2 = NCSCN + 2 AgCl [1a] [1b] Solvent
40 cm3 CH2Cl2
200 cm3 CS2
Amounts of the reactants
1.813 g AgCN, 0.4 cm3 SCl2
26.5 g AgCN, 10.0 cm3 SCl2
Time of the reaction
60 min
30 min
Temperature during the reaction
0 °C
30 °C
[1a] C. J. Burchell, et al., Inorg. Chem., 45 (2006)
[1b] Z. Kisiel et al.; J. Phys. Chem. A, 117 (2013)

17. MI-IR spectra of NCSCN in argon in krypton
CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ)

18. MI-IR spectra of NCSCN Computeda Experimental Assignment Ar matrix
Kr matrix
KBr pellet [1a]
KBr pellet [2]
2666 (0.3)
(2) -
ν3 + ν1
2527 (0.3)
(3)
(2)
ν6 + ν1
2527 (0.4)
(2)
(3)
ν7 + ν5
2487 (0.2)
(1)
(1)
ν9 + ν1
2476 (0.2)
(2)
(1)
ν9 + ν7
2185 (0.3)
(2),
(2)
(3)
ν1 CN str.
2171 (0.1)
(4),
(7)
(8)
2184 vs
2180 s
ν7 CN str.
967 (0.1)
948.6 (3)
ν9 + ν2
651 (2)
680.1 (100)
678.3 (100)
697 m
685 m
ν8 CS str.
650 (7)
677.1 (56)
676.3 (52)
670 m
ν2 CS str.
487 (1)
465 w
ν3 SCN bend.
a (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ))

19. Photolysis of NCSCN in argon
254 nm photo. – deposited
BBUV – 254 nm photo.
and d) NCNCS and NCSNC (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ))

20. Photolysis of NCSCN in argon
Wavenumber / cm–1
k / min–1
1185.0  ±
1994.9  ±
2256.6  ±
2367.4 ±
2689.6  ±
2045.7 ±
690.8 ±
673.1 ±

21. Photolysis of NCSCN in krypton
254 nm photo. – deposited
BBUV – 254 nm photo.
and d) NCNCS and NCSNC (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ))

22. Photolysis of NCSCN: NCSNC
Computeda
Experimental
Assignment
Ar matrix
Kr matrix
2161 (0.7) -
ν1 CN str.
2033 (217)
(68), (32)b
(100)
ν2 NC str.
750 (14)
2ν8
728 (28)
690.8 (12)
691.2 (1)
ν9 + ν5
679 (11)
673.1 (4)
689.1 (2)
ν4 NS str.
630 (20)
ν3 SC str.
457 (3)
ν5 SCN bend.
358 (2) c
ν8 SCN bend.
242 (0.01)
ν9 SNC bend.
239 (2)
ν6 SNC bend.
110 (6)
ν7 NSN def.
CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-cc-pVTZ)
Site split bands.
Not in the measured spectral region.

23. Photolysis of NCSCN: NCNCS
Computeda
Experimental
Assignment
Ar matrix
Kr matrix
gas [d]
gas [e]
2675 (38)
(3)
(3) -
ν4 + ν2
2355 (89)
(2)
(3)
2ν3
2247 (459)
(32)
(42)
2260.9
2240
ν1 NC str.
2013 (1229)
(94), (6)b
(100)
2016.4
1920
ν2 NC str.
1177 (17)
(0.7)
(0.8)
1105
ν3 CS str.
658 (3)
ν4 CN str.
470 (40)
ν5 NCN bend.
447 (3)
ν8 NCN bend.
442 (10)
ν6 NCS bend.
423 (7)
ν9 NCS bend.
84 (4) c
ν7 CNC def.
CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions
(IR intensities: harmonic CCSD(T)/aug-cc-pVTZ)
b) Site split bands. c) Not in the measured spectral region.
d) DeVore, T. C. J. Mol. Struct. 1987, 162, 287.
e) Neidlein R.; Reuter, H. G. Arch. Pharm. 1975, 308, 189.

24. Preparation of NCSeCN [2]
KNCSe + CH3COOAg = AgNCSe + CH3COOK
AgNCSe + I2 = NCSeSeCN + 2 AgI 2 NCSeSeCN = NCSeCN + (NCSe)2Se
Raman spectrum of NCSeCN:
MS spectrum of NCSeCN:
[2] F. Cataldo, Polyhedron, 19 (2000)

25. MI-IR spectra of NCSeCN
in argon
in krypton
CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ)

26. MI-IR spectra of NCSeCN
Comp.a
Experimental
Assignment Ar Kr
KBr pellet [d]
2704 (0.1)
(1) -
ν2 + ν1
2613 (0.2)
(1)
(2)
ν3 + ν1
2495 (0.4)
(0.7)
(1)
ν7 + ν5
2489 (0.3)
(4)
(0.8)
ν6 + ν1
2455 (0.1)
(1)
(1)
ν9 + ν1
2447 (0.2)
(2)
(1)
ν9 + ν7
2176 (2)
(5), (20)b
(5), (10)b
2183 m
ν1 CN str.
2168 (1)
(10)
(2), (4)b
2175 m
ν7 CN str.
581 (5)
573.6 (14)
573.1 (11)
2ν9
547 (6)
527.5 (1), (62), (37)b
523.0 (18), (21), (35), (26)b
516 vs
ν8 CSe str.
528 (6)
522.6 (17), (1)b
520.8 (14), (1)b
ν2 CSe str.
439 (1)
436 m
ν3 SeCN b.
CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-cc-pVTZ)
Site split bands.
Not in the measured spectral region.
E. E. Aynsley, N. N. Greenwood, J. Sprague; J. Chem. Soc., (1964) 704.

27. Photolysis of NCSeCN in argon
254 nm photo. – deposited
BBUV – 254 nm photo.
and d) NCNCS and NCSNC (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ))

28. Photolysis of NCSeCN in krypton
254 nm photo. – deposited
BBUV – 254 nm photo.
and d) NCNCS and NCSNC (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ))

29. Photolysis of NCSeCN: NCSeNC
Computeda
Experimental
Assignment
Ar matrix
Kr matrix
2160 (2) -
ν1 CN str.
2039 (241)
(49), (51)b
2047.5
ν2 NC str.
551 (17)
ν3 SeC str.
533 (14)
ν4 NSe str.
406 (2)
ν5 SeCN bend.
325 (2) c
ν8 SeCN bend.
220 (0.004)
ν9 SeNC bend.
215 (2)
ν6 SeNC bend.
97 (5)
ν7 NSeN def.
CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-cc-pVTZ)
Site split bands.
Not in the measured spectral region.

30. Photolysis of NCSeCN: NCNCSe
Computeda
Experimental
Assignment
Kr matrix
2257 (617)
(52)
ν1 NC str.
2012 (1232)
(89), (11)
ν2 NC str.
1106 (16) -
ν3 CSe str.
510 (3)
ν4 CN str.
434 (28)
ν8 NCN bend.
429 (8)
ν5 NCN bend.
404 (17) b
ν6 NCSe bend.
387 (0.3)
ν9 NCSe bend.
65 (5)
ν7 CNC def.
CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-cc-pVTZ)
Not in the measured spectral region.

31. Outline of the presentation
Introduction, goals of our studies
Computational results
Experimental results
Summary

32. Summary

33. Thank you for your attention!

35. Instruments Matrix-isolation setup: Lowest temperature: 8 K
Cryostat: Closed-cycle He (Air Products Displex DE 202)
Windows: CsI (for IR), NaCl (for UV)
IR spectrometer:
Type: IFS 28 FT-IR
Source: Globar
Detector: DTGS
Best resolution: 1 cm-1
Lamp: Cathodeon HPK
125 W high-pressure
Hg lamp +
Melles Griot
interference filters

36. UV excitation energiesa – [2C, 2N, S]
NCNCS
NCSCN
NCCNS
NCSNC
NCC(NS)
CNNCS
CNCNS
CNC(NS)
CNSNC
286 (0.0000)
231 (0.0016)
364 (0.0000)
267 (0.0003)
456 (0.0040)
343 (0.0003)
354 (0.0000)
485 (0.0005)
281 (0.0000)
261 (0.0001)
206 (0.0002)
203 (0.0019)
345 (0.0024)
262 (0.0028)
347 (0.0000)
313 (0.0040)
215 (0.0032)
245 (0.0001)
213 (1.3034)
249 (0.0007)
218 (0.0005)
226 (1.1834)
237 (0.0003)
206 (0.0048)
235 (0.0000)
224 (0.0054)
218 (0.0003)
209 (0.0483)
201 (0.0416)
213 (0.0501)
EOMEE-CCSD/aug-cc-pVTZ excitation energies
(oscillator strengths: TD-DFT B3LYP/aug-cc-pVTZ)

37. UV excitation energiesa – [2C, 2N, Se]
NCNCSe
NCSeCN
NCCNSe
NCSeNC
NCC(NSe)
CNNCSe
CNCNSe
CNC(NSe)
CNSeNC
311 (0.0000)
255 (0.0000)
395 (0.0000)
200 (0.0002)
263 (0.0003)
220 (0.0001)
206 (0.0000)
273 (0.0003)
313 (0.0000)
290 (0.0001)
212 (0.0026)
388 (0.0000)
203 (0.0000)
232 (0.0001)
276 (0.0001)
247 (0.0000)
201 (0.0000)
245 (1.0828)
206 (0.0762)
EOMEE-CCSD/aug-cc-pVTZ excitation energies
(oscillator strengths: TD-DFT B3LYP/aug-cc-pVTZ)

38. Raman wavenumbers and intensitiesa – [2C, 2N, S]
NCNCS
NCSCN
NCCNS
NCSNC
NCC(NS)
2247 (411)
2181 (100)
2229 (516)
2161 (81)
2238 (139)
2013 (6)
2171 (30)
2085 (19)
2033 (68)
1705 (59)
1177 (26)
650 (22)
1073 (1)
679 (23)
961 (47)
658 (75)
649 (1)
558 (79)
630b (15)
631 (66)
470 (16)
487 (19)
377 (2)
457b (23)
513 (5)
447 (12)
359 (8)
372 (59)
358 (6)
506 (41)
442 (23)
349 (4)
77 (61)
242 (18)
363 (126)
423 (2)
309 (0.1)
239 (7)
220 (9)
84 (273)
120 (190)
110 (228)
164 (95)
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharm. contributions
b) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/cc-pVDZ anharm. contributions
(Raman intensities: B3LYP/aug-cc-pVTZ)

39. Raman wavenumbers and intensities – [2C, 2N, S]
CNNCSa
CNCNSb
CNSNCa
CNC(NS)a
2097 (352)
2291 (532)
2032 (147)
2084 (171)
1891 (5)
2010 (432)
2003 (45)
1698 (51)
1094 (32)
1108 (1)
693 (27)
1038 (45)
719 (23)
564 (62)
685 (4)
668 (61)
522 (94)
349 (28)
414 (31)
486 (50)
418 (0.03)
266 (91)
255 (25)
479 (2)
308 (38)
70 (15)
244 (5)
327 (105)
273 (33)
195 (8)
170 (18)
111 (336)
105 (259)
143 (101)
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharm. contributions
b) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers
(Raman intensities: B3LYP/aug-cc-pVTZ)

40. Raman wavenumbers and intensitiesa – [2C, 2N, Se]
NCNCSe
NCSeCN
NCCNSe
NCSeNC
NCC(NSe)
2257 (531)
2176 (95)
2222 (650)
2160 (80)
2233 (165)
2012 (10)
2168 (34)
2088 (18)
2039 (55)
1702 (54)
1106 (13)
547 (46)
1003 (1)
551 (83)
930 (56)
510 (122)
528 (7)
406 (91)
533 (35)
587 (57)
434 (15)
439 (22)
393 (64)
406 (18)
501 (4)
429 (0.7)
330 (8)
352 (0.3)
325 (7)
434 (87)
404 (0.9)
316 (8)
94 (4)
220 (31)
350 (137)
387 (6)
282 (0.3)
215 (7)
217 (15)
65 (3)
104 (206)
97 (276)
142 (110)
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharm. contributions
b) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/cc-pVDZ anharm. Contributions
(Raman intensities: B3LYP/aug-cc-pVTZ)

41. Raman wavenumbers and intensitiesa – [2C, 2N, Se]
CNNCSe
CNCNSe
CNSeNC
CNC(NSe)
2109 (467)
2226 (702)
2040 (112)
2092 (211)
1859 (9)
1972 (565)
2017 (42)
1702 (48)
1023 (24)
1033 (5)
565 (105)
1002 (43)
619 (11)
369 (65)
549 (27)
605 (88)
444 (142)
334 (76)
346 (20)
457 (1)
380 (0.07)
275 (33)
229 (38)
420 (84)
299 (44)
96 (16)
219 (14)
303 (106)
270 (41)
179 (14)
172 (26)
99 (398)
94 (325)
132 (124)
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharm. contributions
(Raman intensities: B3LYP/aug-cc-pVTZ)

42. Relative Raman intensities
V. Krishnakumar, G. Keresztury, T. Sundius, R. Ramasamy, J. Mol. Struct. 2004, 702, 9–21.

43. Computeda
Experimental (NCSCN)
Assignment
Ar matrix
Kr matrix
KBr pellet [5a]
KBr pellet [6]
2666 (0.3)
(2) -
ν3 + ν1
2527 (0.3)
(3)
(2)
ν6 + ν1
2527 (0.4)
(2)
(3)
ν7 + ν5
2487 (0.2)
(1)
(1)
ν9 + ν1
2476 (0.2)
(2)
(1)
ν9 + ν7
2185 (0.3)
(2),
(2)
(3)
ν1 CN str.
2171 (0.1)
(4),
(7)
(8)
2184 vs
2180 s
ν7 CN str.
967 (0.1)
948.6 (3)
ν9 + ν2
651 (2)
680.1 (100)
678.3 (100)
697 m
685 m
ν8 CS str.
650 (7)
677.1 (56)
676.3 (52)
670 m
ν2 CS str.
487 (1)
465 w
ν3 SCN bend.
359 (0.0)
ν5 SCN bend.
349 (4)
379 m
ν6 SCN bend.
309 (2)
ν9 SCN bend.
120 (8)
ν4 CSC def.
a (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ))

44. Photolysis of NCSCN in krypton
Wavenumber / cm–1
k / min–1
1185.6  ±
1995.8
2251.7  ±
2368.0 ±
2683.1  ±
2043.1* ±
* Fitted only in the 0 – 2040 min region.

45. Emission spectrum of S2

46. MI-UV spectrum of NCSCN

47. NCSeCN
Comp.a
Observed
Assignment Ar Kr
KBr pellet [6]
KBr pellet [d]
2704 (0.1)
(1) -
ν2 + ν1
2613 (0.2)
(1)
(2)
ν3 + ν1
2495 (0.4)
(0.7)
(1)
ν7 + ν5
2489 (0.3)
(4)
(0.8)
ν6 + ν1
2455 (0.1)
(1)
(1)
ν9 + ν1
2447 (0.2)
(2)
(1)
ν9 + ν7
2176 (2)
(5), (20)b
(5), (10)b
2181 s
2183 m
ν1 CN str.
2168 (1)
(10)
(2), (4)b
2175 m
ν7 CN str.
581 (5)
573.6 (14)
573.1 (11)
2ν9
547 (6)
527.5 (1), (62), (37)b
523.0 (18), (21), (35), (26)b
507 vvs
516 vs
ν8 CSe str.
528 (6)
522.6 (17), (1)b
520.8 (14), (1)b
ν2 CSe str.
439 (1)
436 w
436 m
ν3 SeCN b.
330 (0)
345 w
ν5 SeCN b.
316 (3)
336 s
ν6 SeCN b.
282 (1)
312 w
ν9 SeCN b.
104 (7) c
ν4 CSeC def.
CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/aug-cc-pVTZ)
Site split bands.
Not in the measured spectral region. d) E. E. Aynsley, N. N. Greenwood, J. Sprague; J. Chem. Soc., (1964) 704.

48. References – [H, C, N, X]
[3a] M.E. Jacox, D.E. Milligan, J. Chem. Phys. 40 (1964) 2457.
[3b] V.E. Bondybey, J.H. English, C.W. Mathews, R.J. Contolini, J. Mol. Spectrosc. 92 (1982) 431.
[3c] J.H. Teles, G. Maier, B.A. Hess, L.J. Schaad, M. Winnewisser, B.P. Winnewisser, Chem. Ber. 122 (1989) 753.
[3d] J.N. Crowley, J.R. Sodeau, J. Phys. Chem. 93 (1989) 3100.
[3e] M. Pettersson, L. Khriachtchev, S. Jolkkonen, M. Räsänen, J. Phys. Chem. A 103 (1999) 9154.
[3f] M. Mladenovic, M. Lewerenz, M.C. McCarthy, P. Thaddeus, J. Chem. Phys. 131 (2009)
[3g] M. Wierzejewska, J. Moc, J. Phys. Chem. A 107 (2003)
[3h] J.R. Durig, D.W. Wertz, J. Chem. Phys. 46 (1967) 3069.
[3i] M. Wierzejewska, Z. Mielke, Chem. Phys. Lett. 349 (2001) 227.
[3j] T. Pasinszki, M. Krebsz, G. Bazsó, G. Tarczay, Chem. Eur. J. 15 (2009) 6100.
[3k] B. M. Landsberg, Chem. Phys. Lett. 60 (1979) 265.
[3l] J. Vogt, M. Winnewisser, Ber. Bunsen-Ges. 88 (1984) 439.
[3m] J. Vogt, M. Winnewisser, Ber. Bunsen-Ges. 88 (1984) 444.
[3m] M. Krebsz, G. Májusi, B. Pacsai, G. Tarczay, T. Pasinszki, Chem.–Eur. J. 18 (2012) 2646.
[3n] T. Vörös, G. Bazsó, G. Tarczay, J. Phys. Chem. A 117 (2013)

49. References – [2C, 2N, 2X]
[4a] T. Pasinszki, Phys. Chem. Chem. Phys. 10 (2008) 1411.
[4b] A. Schulz, T.M. Klapötke, Inorg. Chem. 35 (1996) 4791.
[4c] G. Maier, M. Naumann, H.P. Reisenauer, J. Eckwert, Angew. Chem. Int. Ed. 35 (1996) 1696.
[4d] Ch. Grundmann, Angew. Chem. Int. Ed. 2 (1963) 260.
[4e] Ch. Grundmann, V. Mini, J.M. Dean, H.-D. Frommeld, Justus Liebigs Ann. Chem. 687 (1965) 191.
[4f] G. Maier, J.H. Teles, Angew. Chem. Int. Ed. 26 (1987) 155.
[4g] T. Pasinszki, N.P.C. Westwood, J. Am. Chem. Soc. 117 (1995) 8425.
[4h] B. Guo, T. Pasinszki, N.P.C. Westwood, P.F. Bernath, J. Chem. Phys. 103 (1995) 3335.
[4i] T. Vörös, G. Bazsó, Gy. Tarczay, T. Pasinszki, J. Mol. Structure, 1025 (2012) 117.
[4j] E. Söderbäck, Liebigs. Ann. Chem. 419 (1919) 21.
[4k] F. Seel, D. Wesemann, Chem. Ber. 86 (1953) 1107.
[4l] F. Seel, D. Wesemann, Chem. Ber. 88 (1955) 1747.
[4m] F. Cataldo, J. Inorg. Organomet. Polym. 7 (1997) 35.
[4n] A.J. Barnes, S. Suzuki, in: W.F.Murphy (Ed.), Proceedings of the 7th International Conference Raman Spectroscopy, Ottawa, 1980, North-Holland, Amsterdam, 1980, p. 186.
[4o] F. Cataldo, Polyhedron 19 (2000) 681.
[4p] C. J. Burchell et. al., Inorg. Chem. 45 (2006) 710.

50. References – [2C, 2N, X] F. Cataldo, Polyhedron 19 (2000) 681.
C. J. Burchell, et. al., Inorg. Chem. 45 (2006) 710.
Feher, Miklos; Pasinszki, Tibor; Veszpremi, Tamas Inorg. Chem., 34 (1995) 945.
W. H. Hocking and M. C. L. Gerry, J. Mol. Spectrosc., 59 (1976) 338.
W. H. Hocking and M. C. L. Gerry, J. Chem. Sot. Chem. Commun., (1973) 47.
B. Bak, H. Svanholt and A. Holm, Acta Chem. Stand., Ser. A., 33 (1979) 597.
D. C. Frost, H. W. Kroto, C. A. McDowell and N. P. C. Westwood, J. Electron.
Spectrosc. Relat. Phenom., 11 (1977) 147.
Mayer, E, Monatsh. Chem., 101 (1970) 834.
DeVore, T.C., J. Mol. Struct., 162 (1987) 287.
Pasinszki, T.; Westwood, N.P.C., J. Phys. Chem., 42 (1996)
Guo, B.; Pasinszki, T.; Westwood, N.P.C.; Zhang, K.; Bernath, P.F.,J. Chem. Phys., 105 (1996) 4457.
Brupbacher, Th.; Bohn, R.K.; Jager, W.; Gerry, M.C.L.; Pasinszki, T., Westwood, N.P.C., J. Mol. Spectrosc., 181 (1997) 316.
Maier, G.; Teles, J. H. Angew. Chem. 99 (1987) 152.
Hand, C. W.; Hexter, R. M. J. Am. Chem. Soc. 92 (1970) 1828.
Zbigniew Kisiel, Manfred Winnewisser, B. P. Winnewisser, F. C. De Lucia, D. W. Tokaryk, B. E. Billinghurst, J. Phys. Chem. A 117 (2013) 13815

51. References – [2C, 2N, X]
Cataldo, Franco; Keheyan, Yeghis; Polyhedron; 21 (2002) 1825.
King, Michael A.; Kroto, Harold W.; J. Am. Chem. Soc. 106 (1984) 7347.
Jemson, H. M.; Gerry, M. C. L.; J. Mol. Spectr. 124 (1987) 481.
Il'in, A. P.; Eremin, L. P.; Il'ina, T. P.; Russian Journal of Inorganic Chemistry (Translation of Zhurnal Neorganicheskoi Khimii);26 (1981) 913.
Klapotke, T. M.; Krumm, B.; Galvesz-Ruiz, J. C.; Noth, H.; Schwab, I. Eur. J. Inorg. Chem. 24 (2004) 4764.
King, Michael A.; Kroto, Harold W., J. Chem. Soc., Chem. Comm. 13 (1980) 606.
King, M.A.; Kroto, H.W.; Landsberg, B.M., J. Mol. Spectrosc., 113 (1985) 1.
M. Krebsz, Gy. Tarczay, T. Pasinszki, Chem. Eur. J. 19 (2013)
Aynsley et al.; J. Chem. Soc. (1964) 704.
Linke, K. H.; Lemmer, F. Z. Anorg. Allg. Chem. 345 (1966) 211.
M. Krebsz, G. Majusi, B. Pacsai, Gy. Tarczay, T. Pasinszki Chemistry, A European Journal 18 (2012) 2646.