Matrix Isolation and Computational
Study of [2C, 2N, X] (X = S, Se) Isomers
Tamás Vörös, György Tarczay
Institute of Chemistry, Eötvös University
Budapest, Hungary
Outline of the presentation
• Introduction, goals of our studies
• Computational results
• Experimental results
• Summary
Outline of the presentation
• Introduction, goals of our studies
• Computational results
• Experimental results
• Summary
Introduction
• Early 19th century:
Wöhler: Ag-cyanate (AgOCN)
Isomerism
(Berzelius)
Liebig: Ag-fulminate (AgCNO)
• Presently:
HNCX HXCN HCNX HXNC
X=O
X=S
X = Se
!
!
!
Introduction
Sgr B2:
HNCO
HOCN
HNCS
HSCN
TCM-1:
HCNO
Introduction
NCNCX
NCCNX
NCXCN
NCXNC
X=O
!
!
X=S
X = Se
[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) 710-716.
[1b] Z. Kisiel et al.; J. Phys. Chem. A, 117 (2013) 13815-13824.
[2] F. Cataldo, Polyhedron, 19 (2000) 681-688.
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
Outline of the presentation
• Introduction, goals of our studies
• Computational results
• Experimental results
• Summary
Equilibrium structuresa, relative energiesb
a
CCSD(T)/aug-cc-pVTZ
b ΔE (CCSD(T)/aug-cc-pVTZ) + ΔZPVE (CCSD(T)/aug-cc-pVTZ)
Equilibrium structures
NCCNO
CNCNS
NCNCSe
MP2/6-31G*
[3]
bent,
quasilinear
bent
linear
CCSD(T)/
aug-cc-pVTZ
linear
linear
bent
[3] M. Feher, T. Pasinszki, T. Veszpremi, Inorg. Chem., 34 (1995) 945-951.
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)
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)
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)
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)
Outline of the presentation
• Introduction, goals of our studies
• Computational results
• Experimental results
• Summary
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) 710-716.
[1b] Z. Kisiel et al.; J. Phys. Chem. A, 117 (2013) 13815-13824.
MI-IR spectra of NCSCN
a) in argon
b) in krypton
c) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic
contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ)
MI-IR spectra of NCSCN
Experimental
Computeda
KBr
pellet [2]
Assignment
Ar matrix
Kr matrix
KBr pellet
[1a]
2666 (0.3)
2681.4 (2)
-
-
-
ν3 + ν1
2527 (0.3)
2542.2 (3)
2538.3 (2)
-
-
ν6 + ν1
2527 (0.4)
2540.9 (2)
2536.2 (3)
-
-
ν7 + ν5
2487 (0.2)
2502.1 (1)
2498.3 (1)
-
-
ν9 + ν1
2476 (0.2)
2491.3 (2)
2487.3 (1)
-
-
ν9 + ν7
2185 (0.3)
2192.9 (2),
2190.2 (2)
2188.9 (3)
-
-
ν1 CN str.
2171 (0.1)
2181.9 (4),
2178.8 (7)
2177.8 (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))
Photolysis of NCSCN in argon
a) 254 nm photo. – deposited
b) BBUV – 254 nm photo.
c) and d) NCNCS and NCSNC (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers +
CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/augccpVTZ))
Photolysis of NCSCN in argon

A  A0  1  e
 kt

Wavenumber /
cm–1
k / min–1
1185.0
0.00063 ±
0.00002
1994.9
0.00065 ±
0.00002
2256.6
0.00065 ±
0.000005
2367.4
0.00060 ±
0.00006
2689.6
0.00065 ±
0.00004
2045.7
0.00106 ±
0.000009
690.8
0.00097 ±
0.00006
673.1
0.00101 ±
0.00003
Photolysis of NCSCN in krypton
a) 254 nm photo. – deposited
b) BBUV – 254 nm photo.
c) and d) NCNCS and NCSNC (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers +
CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/augccpVTZ))
Photolysis of NCSCN: NCSNC
Computeda
Experimental
Assignment
Ar matrix
Kr matrix
2161 (0.7)
-
-
ν1 CN str.
2033 (217)
2045.7 (68), 2043.4 (32)b
2043.1 (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
c
ν8 SCN bend.
242 (0.01)
c
c
ν9 SNC bend.
239 (2)
c
c
ν6 SNC bend.
110 (6)
c
c
ν7 NSN def.
a) 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.
Photolysis of NCSCN: NCNCS
Computeda
Experimental
Assignment
Ar matrix
Kr matrix
gas [d]
gas [e]
2675 (38)
2689.6 (3)
2683.1 (3)
-
-
ν4 + ν2
2355 (89)
2367.4 (2)
2368.0 (3)
-
-
2ν3
2247 (459)
2256.6 (32)
2251.7 (42)
2260.9
2240
ν1 NC str.
1995.8
(100)
2016.4
1920
ν2 NC str.
2013 (1229) 1994.9 (94), 1992.1 (6)b
1177 (17)
1185.0 (0.7)
1185.6 (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
c
c
c
ν7 CNC def.
a) 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.
Preparation of NCSeCN [2]
a)
KNCSe + CH3COOAg = AgNCSe + CH3COOK
b)
AgNCSe + I2 = NCSeSeCN + 2 AgI
2 NCSeSeCN = NCSeCN + (NCSe)2Se
Raman spectrum of NCSeCN:
[2] F. Cataldo, Polyhedron, 19 (2000) 681-688.
MS spectrum of NCSeCN:
MI-IR spectra of NCSeCN
a) in argon
b) in krypton
c) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic
contributions (IR intensities: harmonic CCSD(T)/aug-ccpVTZ)
MI-IR spectra of NCSeCN
Comp.a
Experimental
Assignment
Ar
Kr
KBr pellet [d]
2704 (0.1)
2699.3 (1)
-
-
ν2 + ν1
2613 (0.2)
2619.6 (1)
2617.7 (2)
-
ν3 + ν1
2495 (0.4)
2510.2 (0.7)
2499.8 (1)
-
ν7 + ν5
2489 (0.3)
2502.6 (4)
2497.0 (0.8)
-
ν6 + ν1
2455 (0.1)
2464.7 (1)
2462.0 (1)
-
ν9 + ν1
2447 (0.2)
2455.7 (2)
2453.4 (1)
-
ν9 + ν7
2176 (2)
2186.3 (5), 2183.1 (20)b
2182.7 (5), 2181.6 (10)b
2183 m
ν1 CN str.
2168 (1)
2174.0 (10)
2173.9 (2), 2172.3 (4)b
2175 m
ν7 CN str.
581 (5)
573.6 (14)
573.1 (11)
-
2ν9
547 (6)
527.5 (1), 526.1 (62),
524.4 (37)b
523.0 (18), 524.2 (21),
525.4 (35), 526.7 (26)b
516 vs
ν8 CSe str.
528 (6)
522.6 (17), 521.0 (1)b
520.8 (14), 519.3 (1)b
-
ν2 CSe str.
439 (1)
-
-
436 m
ν3 SeCN b.
a)
b)
c)
d)
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.
Photolysis of NCSeCN in argon
a) 254 nm photo. – deposited
b) BBUV – 254 nm photo.
c) and d) NCNCS and NCSNC (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers +
CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/augccpVTZ))
Photolysis of NCSeCN in krypton
a) 254 nm photo. – deposited
b) BBUV – 254 nm photo.
c) and d) NCNCS and NCSNC (CCSD(T)/aug-cc-pVTZ harmonic wavenumbers +
CCSD(T)/aug-cc-pVDZ anharmonic contributions (IR intensities: harmonic CCSD(T)/augccpVTZ))
Photolysis of NCSeCN: NCSeNC
Computeda
Experimental
Assignment
Ar matrix
Kr matrix
2160 (2)
-
-
ν1 CN str.
2039 (241)
2055.3 (49), 2049.6 (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
c
ν8 SeCN bend.
220 (0.004)
c
c
ν9 SeNC bend.
215 (2)
c
c
ν6 SeNC bend.
97 (5)
c
c
ν7 NSeN def.
a) 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.
Photolysis of NCSeCN: NCNCSe
Computeda
Experimental
Kr matrix
Assignment
2257 (617)
2260.9 (52)
ν1 NC str.
2012 (1232)
1970.7 (89), 1965.7 (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)
b
ν9 NCSe bend.
65 (5)
b
ν7 CNC def.
a) CCSD(T)/aug-cc-pVTZ harmonic wavenumbers + CCSD(T)/aug-cc-pVDZ anharmonic
contributions (IR intensities: harmonic CCSD(T)/aug-cc-pVTZ)
b) Not in the measured spectral region.
Outline of the presentation
• Introduction, goals of our studies
• Computational results
• Experimental results
• Summary
Summary
NCNCX
NCCNX
NCXCN
NCXNC
X=O
X=S
X = Se
!
!
!
!
!
Thank you for your attention!
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
125 W high-pressure
Source: Globar
Hg lamp +
Detector: DTGS
Best resolution: 1
Lamp: Cathodeon HPK
cm-1
Melles Griot
interference filters
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)
354
(0.0000)
203
(0.0019)
345
(0.0024)
262
(0.0028)
347
(0.0000)
313
(0.0040)
215
(0.0032)
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)
245
(0.0001)
a) EOMEE-CCSD/aug-cc-pVTZ excitation energies
(oscillator strengths: TD-DFT B3LYP/aug-cc-pVTZ)
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)
247
(0.0000)
201
(0.0000)
276
(0.0001)
245
(1.0828)
206
(0.0762)
a) EOMEE-CCSD/aug-cc-pVTZ excitation energies
(oscillator strengths: TD-DFT B3LYP/aug-cc-pVTZ)
232
(0.0001)
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)
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)
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)
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)
Relative Raman intensities
4
~
~
~
~
I i  f ( 0   i ) S i /  i 1  exp  hc i / kT 
V. Krishnakumar, G. Keresztury, T. Sundius, R. Ramasamy, J. Mol. Struct. 2004, 702,
9–21.
Experimental (NCSCN)
Computeda
KBr
pellet [6]
Assignment
Ar matrix
Kr matrix
KBr pellet
[5a]
2666 (0.3)
2681.4 (2)
-
-
-
ν3 + ν1
2527 (0.3)
2542.2 (3)
2538.3 (2)
-
-
ν6 + ν1
2527 (0.4)
2540.9 (2)
2536.2 (3)
-
-
ν7 + ν5
2487 (0.2)
2502.1 (1)
2498.3 (1)
-
-
ν9 + ν1
2476 (0.2)
2491.3 (2)
2487.3 (1)
-
-
ν9 + ν7
2185 (0.3)
2192.9 (2),
2190.2 (2)
2188.9 (3)
-
-
ν1 CN str.
2171 (0.1)
2181.9 (4),
2178.8 (7)
2177.8 (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))
Photolysis of NCSCN in krypton

A  A0  1  e
 kt

Wavenumber /
cm–1
k / min–1
1185.6
0.00066 ±
0.00002
1995.8
0.00066 ±
0.00002
2251.7
0.00052 ±
0.00002
2368.0
0.00068 ±
0.00004
2683.1
0.00069 ±
0.00006
2043.1*
0.00145 ±
0.00005
* Fitted only in the 0 – 2040 min region.
Emission spectrum of S2
MI-UV spectrum of NCSCN
NCSeCN
Observed
Comp.a
Assignment
Ar
Kr
KBr pellet [6]
KBr pellet [d]
2704 (0.1)
2699.3 (1)
-
-
-
ν2 + ν1
2613 (0.2)
2619.6 (1)
2617.7 (2)
-
-
ν3 + ν1
2495 (0.4)
2510.2 (0.7)
2499.8 (1)
-
-
ν7 + ν5
2489 (0.3)
2502.6 (4)
2497.0 (0.8)
-
-
ν6 + ν1
2455 (0.1)
2464.7 (1)
2462.0 (1)
-
-
ν9 + ν1
2447 (0.2)
2455.7 (2)
2453.4 (1)
-
-
ν9 + ν7
2176 (2)
2186.3 (5), 2183.1 (20)b
2182.7 (5), 2181.6 (10)b
2181 s
2183 m
ν1 CN str.
2168 (1)
2174.0 (10)
2173.9 (2), 2172.3 (4)b
-
2175 m
ν7 CN str.
581 (5)
573.6 (14)
573.1 (11)
-
-
2ν9
547 (6)
527.5 (1), 526.1 (62), 524.4
(37)b
523.0 (18), 524.2 (21), 525.4 (35),
526.7 (26)b
507 vvs
516 vs
ν8 CSe str.
528 (6)
522.6 (17), 521.0 (1)b
520.8 (14), 519.3 (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.
c
c
104 (7)
a) 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) E. E. Aynsley, N. N. Greenwood, J. Sprague; J. Chem. Soc., (1964) 704.
ν4 CSeC
def.
References – [H, C, N, X]
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431.
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[4j] E. Söderbäck, Liebigs. Ann. Chem. 419 (1919) 21.
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186.
[4o] F. Cataldo, Polyhedron 19 (2000) 681.
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References – [2C, 2N, X]
•
•
•
•
•
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•
•
•
•
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F. Cataldo, Polyhedron 19 (2000) 681.
C. J. Burchell, et. al., Inorg. Chem. 45 (2006) 710.
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W. H. Hocking and M. C. L. Gerry, J. Mol. Spectrosc., 59 (1976) 338.
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