Absorption Spectrum of 1,2,4-Trichlorobenzene in the Near Ultraviolet

Hedwig Kohn; H. Sponer

doi:10.1364/JOSA.39.000075

Journal of the Optical Society of America
Vol. 39,
Issue 1,
pp. 75-85
(1949)
•https://doi.org/10.1364/JOSA.39.000075

Absorption Spectrum of 1,2,4-Trichlorobenzene in the Near Ultraviolet

Hedwig Kohn and H. Sponer

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Hedwig Kohn and H. Sponer, "Absorption Spectrum of 1,2,4-Trichlorobenzene in the Near Ultraviolet," J. Opt. Soc. Am. 39, 75-85 (1949)

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Abstract

The absorption spectrum of 1,2,4-trichlorobenzene at 2960–2600A has been investigated using a medium Hilger quartz spectrograph. The band system corresponds to a transition A′–A′ (1,2,4-C₆H₃Cl₃ belongs to symmetry group C_s) with the transition moment lying in the molecular plane. The transition is allowed. In agreement with this assignment the 0–0 band appears strongly. Several progressions of symmetric vibrations and many combinations between them have been observed. A number of vibrational frequencies were identified with Raman frequencies. Characteristic of the spectrum is that its bands are spaced very regularly apart from each other, with a difference of about 30 cm⁻¹ being most prominent. These differences represent v–v transitions of low frequency vibrations.

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Symmetry type	Essential elements of symmetry σ_z	Number of vibrations	Selection rules
Symmetry type	Essential elements of symmetry σ_z	Number of vibrations	Raman	Infra-red
A′	+	21 T_xT_y	+	+
A′	−	9 T_z	+	+

Upper state	108	301	333	364

Ground state
200 (R196)	−92	+101	+133	+164
326 (R329)	−218	−25	+7	+38
388 (R397)	−280	−87	−55	−24
461 (R458)	−353	−160	−128	−97

Symmetry type	Essential elements of symmetry σ_z	Number of vibrations	Selection rules
Symmetry type	Essential elements of symmetry σ_z	Number of vibrations	Raman	Infra-red
A′	+	21 T_xT_y	+	+
A′	−	9 T_z	+	+

Upper state	108	301	333	364

Ground state
200 (R196)	−92	+101	+133	+164
326 (R329)	−218	−25	+7	+38
388 (R397)	−280	−87	−55	−24
461 (R458)	−353	−160	−128	−97

Wave numbers	Intensity	Separation from 0–0 band	Assignments	Remarks
33,824	ew	−1284		Reservoir at 82°C. Bands from 33824 to 34605 are very weak and very difficult to measure. Hence these wave number values are less reliable than those above 34605.
856	ew	−1252	0−1161−90
887	ew	−1221	0−1161−60; 0−1132−90
916	ew	−1192	0−1161−30; 0−1132−60;
			0−1101−90
947	ew	−1161	0−1161; 0−1101−60;	R 1155
			0−1132−30
976	ew	−1132	0−1132; 0−1101−30	R 1132
34,007	ew	−1101	0−1101	R 1098
042	ew	−1066	0−1035−30;0−680−388
	observed		0−1035	R 1035
130	ew	−978	0−3×326; 0−sep. 878−98
165	ew	−943	0−sep. 878−60
196	ew	−912	0−sep. 878−30
230	vw	−878	0−200−680
268	vw	−840	0−808−30
300	w	−808	0−808?	R 815
335	w	−773	0−680−90; 0−2×388	Very uncertain.
53	w	−755		Very uncertain.
368	m	−740	0−680−60; 0−sep. 653−90
394	m	−714	0−680−30; 0−sep. 653−60
408	m	−700
428	m	−680	0−680; 0−sep. 653−30;	R 676
			0−sep. 591−90
455	w	−653	0−2×326
471	w	−637
501	m	−607
517	m	−591	0−200−388; 0−sep. 530−60
539	m	−569	0−sep. 530−30; 0−680+108
565	st	−543
578	st	−530	0−200−326
605	st	−503		Uncertain value.

				Reservoir at 65°C and 70°C. Change in intensity scale.
630	ewd	−478	0−388−90	Uncertain value.
647	ewd	−461	0−461	Uncertain value.
				R 458
686	ewd	−422	0−388−30; 0−326−98
696	ewd	−412	0−326−90
720	ew	−388	0−388; 0−326−60	Inaccurate, difficult to measure.
				R 397
749	vw	−359	0−326−30
782	w-m	−326	0−326	R 329
808	w-m	−300	0−300?	R 308
838	w-m	−270
876	m	−232	0−200−30
891*	st	−217
908*	st	−200	0−200	R 196
				Bands with an asterisk were also measured from plate taken in large Hilger. 34891/908 are probably two different bands, measured as single at 34909 in medium Hilger.
939*	w-m	−169		Bands from 34908 to 35108 are the sharpest in the spectrum.
948*	w-m	−160	0−461+301
981	st	−127	0−461+333
35,004*	st	−104		Probably two different bands.
010*	st	−98	0−98
043*	vst	−65	0−60	Probably two heads of same band. Measured single at 35050 in medium Hilger.
048*	vst	−60	0−60
072*	vst	−36	0−30	Probably two heads of same band. Measured single at 35080 in medium Hilger.
078*	vst	−30	0−30
093*	st	−15
102*	vst	−6	0−0 band main edge	Probably two heads of same band. Measured single at 35108 in medium Hilger.
108*	est	0	0−0 band main edge
148	vw-w	+40	0−326+364
183	ew	+75	0+108−30
216	vw	108	0+108
35,249	vw	141	0+sep. 169−30
277	ewd	169	0−200+364; 0−461+629	Uncertain, difficult to measure.
310	ew	202	0−200−326+2×364
341	ew	233	0−388+629; 0+333−98
374	vw	266	0+301−30; 0+333−60;
			0+364−98; 0−461+2×364
409	vw	301	0+301; 0+333−30;
			0+364−60; 0−326+629
441	vw	333	0+333; 0+364−30
472	vw-w	364	0+364
503	vw	395
515	vw	407	0+108+301
538	vwd	430	0−200+629	Perhaps three overlapping bands.
42		434
46		438	0+108+333
575	vw	467	0+108+364; 0−sep. 160+629
606	w	498	0−sep. 127+629
641	w-m	533	0+629−98; 0−461+sep. 997
676	w-m	568	0+629−60
706	m	598	0+629−30; 0+2×301;
			0−388+364+629;
			0−388+997
737	m-s	629	0+629; 0+301+333
751	w	643	0−200+2×108+629
772	ewd	664	0+2×333; 0+301+364;	Bands from 35772 to 35863 very difficult to measure because of strong background absorption.
			0−326+997
803	ewd	695	0+333+364;
			0−680+301+1074;
			0−300+997
834	ewd	726	0+2×364;
			0−680+333+1074;
			0−680+301+1100
863	ewd	755	0−680+333+1100;
			0−680+301+1128;
			0−680+364+1074
888	vwd	780	0−326+108+997
919	wd	811	0+997−98−90	Perhaps two bands overlapping.
945	vwd	837	0+997−98−60
979	m	871	0+997−98−30;
			0−sep. 127+997
36,011	m-s	903	0+997−98; 0−200+1100
044	m-s	936	0+997−60; 0+301+629
075	s	967	0+997−30; 0+333+629
105	vs	997	0+997; 0+364+629;
			0+1100−104
121	m-s	1013	0+1074−60; 0+1100−90
148	m-s	1040	0+1074−30; 0+1100−60;	Possibly two heads of same band.
154	s	1046	0+1128−90
178*	es	1070	0+1074; 0+1100−30;	Probably two heads of same band. Bands with an asterisk have been measured from plates in large and medium Hilger.
182*	es	1074	0+1128−60
208*	vs	1100	0+1100; 0+108+997;
			0+1128−30
228*	s	1120	0+1128	Probably two heads of same band.
236*	s	1128	0+1128	Probably two heads of same band.
251	vw	1143	0+sep. 1205−60;
			0+sep. 1235−90
280	ewd	1172	0+sep. 1205−30;	Bands from 36280 to 36343 measured from one plate only since very weak and diffuse.
			0+sep. 1235−60;
			0+sep. 1263−90;
			0+sep. 169+997
313	vwd	1205	0+sep. 1235−30;
			0+sep. 1263−60;
			0+sep. 202+997;
			0+108+1100
343	ewd	1235	0+sep. 1263−30;
			0+sep. 233+997;
			0+108+1128
371	vwd	1263	0+sep. 1296−30;
36,371			0+sep. 266+997;
			0+2×629
404	ewd	1296	0+sep. 1329−30;
			0+301+997
437	vw	1329	0+sep. 1359−30;
			0+333+997
467	m-w	1359	0+364+997; 0+2×364+629
478	w	1370	0+sep. 1401−30;
			0+sep. 1433−60;
			0+sep. 1463−90;
			0+301+1074
509	vw	1401	0+sep. 1433−30;
			0+sep. 1463−60;
			0+sep. 407+997;
			0+301+1100; 0+333+1074
541	m-w	1433	0+sep. 1463−30;
			0+sep. 1495−60;
			0+sep. 434+997;
			0+301+1128;
			0+333+1100; 0+364+1074
571	m-w	1463	0+sep. 1495−30;
			0+sep. 467+997;
			0+333+1128; 0+364+1100
603	vwd	1495	0+sep. 1595−98;
			0+sep. 498+997;
			0+364+1128
640	vwd	1532	0+sep. 1564−30;
			0+sep. 1595−60;
			0+sep. 1624−90;
			0+sep. 533+997
672	w	1564	0+sep. 1595−30;
			0+sep. 1624−60;
			0+sep. 568+997;
			0+301+2×629
703	w	1595	0+sep. 1624−30;
			0+sep. 598+997;
			0+333+2×629
732	w	1624	0+629+997;
			0+364+2×629
761	w	1653	0+sep. 1754−98
777	w	1669	0+sep. 1698−30;
			0+sep. 1726−60
806	w-m	1698	0+sep. 1726−30;
			0+sep. 1754−60;
			0+629+1074
834	w	1726	0+sep. 1754−30;
			0+629+1100
862	vw	1754	0+629+1128	Bands from 36862 to 36989 are very difficult to measure, inaccurate.
883	ewd	1775	0+333+364+1074;
			0+sep. 780+997
910	ewd	1802	0+2×364+1074;
			0+333+364+1100
—	observed	—		Too weak and diffuse for measurement.
965	ewd	1857	0+2×364+1128
989	ewd	1881	0+3×629
37,016	ewd	1908	0+2×997−90
045	vwd	1937	0+sep. 936+997
075	vwd	1967	0+sep. 967+997
097	wd	1989	0+sep. 997+997	Perhaps two heads of same band and over lapping of others.
104		1996
115		2007	0+sep. 2038−30;
			0+sep. 2067−60;
			0+sep. 2095−90
146	w-m	2038	0+sep. 2067−30;
			0+sep. 2095−60;
			0+333+629+1074
175	w-m	2067	0+sep. 2095−30;
37,175			0+997+1074;
			0+333+629+1100
203	w-m	2095	0+997+1100;
			0+333+629+1128
228	vwd	2120	0+sep. 2147−30;
			0+sep. 2175−60;
			0+sep. 2206−90;
			0+997+1128
255	vw	2147	0+sep. 2175−30;
			0+sep. 2206−60;
			0+2×1074
283	w	2175	0+sep. 2206−30;
			0+1074+1100
314	w	2206	0+2×1100; 0+1074+1128

339	md	2231	0+sep. 2293−60;	Reservoir at 82°C.
			0+sep. 1235+997;	Change in intensity scale.
—	observed	—	0+1100+1128	Too diffuse for measurement.
382	m-sd	2274	0+sep. 2367−90	Bands from 37382 to 37457 are very diffuse; strong background absorption.
401	m-sd	2293	0+sep. 1296+997;
			0+sep. 2324−30
432	m-sd	2324	0+sep. 1329+997
457	m-sd	2349	0+sep. 1359+997
475	md	2367	0+sep. 1370+997;
			0+sep. 2464−98
509	md	2401	0+sep. 1401+997;
			0+sep. 2464−60;
			0+sep. 2430−30
538	md	2430	0+sep. 1433+997;
			0+sep. 2464−30
547	md	2439	0+sep. 2501−60
572	w-md	2464	0+sep. 1463+997;
			0+sep. 2563−98
609	m	2501	0+sep. 2532−30;
			0+sep. 2563−60;
			0+sep. 2592−90; 0+4×629
640	w-m	2532	0+sep. 1532+997;
			0+sep. 2563−30;
			0+sep. 2592−60;
			0+333+2×1100
671	w-m	2563	0+333+1100+1128;
			0+364+1074+1128;
			0+364+2×1100;
			0+sep. 1564+997;
			0+sep. 2592−30
700	w-m	2592	0+364+1100+1128;
			0+sep. 1595+997;
			0+sep. 2685−90
—	observed	—		Too diffuse to measure.
729	vwd	2621	0+sep. 2685−60;
			0+sep. 2714−90;
			0+sep. 1624+997
765	wd	2657	0+sep. 2685−30;
			0+sep. 2714−60;
			0+301+2×629+1100;
			0+333+2×629+1074
793	wd	2685	0+301+2×629+1128;
			0+333+2×629+1100;
			0+sep. 2714−30
822	vwd	2714	0+333+2×629+1128
845	ewd	2737	0+sep. 2796−60;
			0+2×333+997+1074
868	ewd	2760	0+sep. 2857−98;
			0+2×333+997+1100
904	wd	2796	0+sep. 2829−30;
			0+sep. 2857−60;
37,904			0+sep. 1802+997;
			0+2×333+997+1128
937	wd	2829	0+sep. 2857−30;
			0+629+2×1100;
			0+629+1074+1128
965	wd	2857	0+sep. 1857+997;
			0+629+1100+1128
38,000	vwd	2892	0+sep. 2988−98;
			0+629+2×1128
033	vwd	2925	0+sep. 2988−60
067	vwd	2959	0+sep. 1967+997;
			0+sep. 2988−30;
			0+2×301+2×629+1100;
096	vwd	2988	0+3×997	Perhaps two heads of same band.
103	wd	2995
137	wd	3029	0+sep. 2038+997;
			0−200+997+1100+1128
171	wd	3063	0+sep. 2067+997
213	vwd	3105	0+sep. 3137−30;
			0+sep. 3166−60;
			0−200+1074+1100+1128
245	vw	3137	0+sep. 2147+997;
			0+sep. 3166−30;
			0+5×629
274	vw	3166	0+sep. 2175+997;
			0+sep. 3230−60
307	ewd	3199	0+sep. 3230−30;	Bands from 38307 to the end are inaccurate.
			0+sep. 2206+997
338	ewd	3230	0+3×1074;
			0+sep. 2231+997
—	observed	—		Too weak and diffuse for measurement.
383	ewd	3275	0+1074+2×1100
420	ewd	3312	0+3×1100

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