On the nature of the low-lying singlet states of 4-(Dimethyl-amino)benzonitrile

Journal of the American Chemical Society

Volumn 126, Issue 23, 2004, Pages 7399-7410

  Köhn, Andreas ^a,b   Hättig, Christof ^a  

^a KARLSRUHE INSTITUTE OF TECHNOLOGY   (Germany)

^b AARHUS UNIVERSITY   (Denmark)

Author keywords

[No Author keywords available]

Indexed keywords

ACOUSTIC EMISSIONS; CHARGE TRANSFER; COUPLED CIRCUITS; HARMONIC ANALYSIS; INFRARED SPECTROGRAPHS; OPTIMIZATION;

INTRAMOLECULAR CHARGE-TRANSFER; PROTOTYPE MOLECULE; RAMAN MEASUREMENTS;

FLUORESCENCE;

4 (DIMETHYLAMINO)BENZONITRILE; 4 DIMETHYLAMINOBENZONITRILE; BENZONITRILE; COORDINATION COMPOUND; SINGLET OXYGEN; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL MODEL; CLUSTER ANALYSIS; COUPLED CLUSTER MODEL; CRYSTAL STRUCTURE; ELECTRONICS; FLUORESCENCE; GEOMETRY; INTRAMOLECULAR CHARGE TRANSFER; RAMAN SPECTROMETRY; SURFACE CHARGE; VIBRATION; X RAY DIFFRACTION;

EID: 2942565685     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0490572     Document Type: Article

References (71)

1. Lippert, E.; Lüder, W.; Boos, H. In Advances in Molecular Spectroscopy; Mangini, A., Ed.; Pergamon: Oxford, 1962; pp 443-457.
2. Grabowski, Z. R.; Rotkiewicz, K.; Siemiarczuk, A.; Cowley, D. J.; Baumann, W. Nouv. J. Chim. 1979, 3, 443-454.
3. Rotkiewicz, K.; Grellmann, K. H.; Grabowski, Z. R. Chem. Phys. Lett. 1973, 19, 315-318.
4. Rettig, W. Angew. Chem., Int. Ed. 1986, 25, 971-988.
5. Leinhos, U.; Kühnle, W.; Zachariasse, K. A. J. Phys. Chem. 1991, 95, 2013-2021.
6. Zachariasse, K. A.; von der Haar, T.; Hebecker, A.; Leinhos, U.; Kühnle, W. Pure Appl. Chem. 1993, 65, 1745-1750.
7. von der Haar, T.; Hebecker, A.; Il'ichev, Y.; Jiang, Y.-B.; Kühnle, W.; Zachariasse, K. Recl. Trav. Chim. Pays-Bas 1995, 114, 430-442.
8. Il'ichev, Y. V.; Kühnle, W.; Zachariasse, K. A. J. Phys. Chem. A 1998, 102, 5670-5680.
9. Zachariasse, K. A. Chem. Phys. Lett. 2000, 320, 8-13.
10. Schuddeboom, W.; Jonker, S. A.; Warman, J. M.; Leinhos, U.; Kühnle, W.; Zachariasse, K. A. J. Phys. Chem. 1992, 96, 10809-10819.
11. Gorse, A.-D.; Pesquer, M. J. Phys. Chem. 1995, 98, 4039-4049.
12. Sobolewski, A. L.; Domcke, W. Chem. Phys. Lett. 1996, 259, 119-127.
13. Zachariasse, K.; Druzhinin, S.; Bosch, W.; Machinek, R. J. Am. Chem. Soc. 2004, 126, 1705-1715.
14. Serrano Andrés, L.; Merchán, M.; Roos, B. O.; Lindh, R. J. Am. Chem. Soc. 1995, 117, 3189-3204.
15. Sobolewski, A. L.; Sudholt, W.; Domcke, W. J. Phys. Chem. A 1998, 102, 2716-2722.
16. Sudholt, W.; Sobolewski, A. L.; Domcke, W. Chem. Phys. 1999, 240, 9-18.
17. Sudholt, W.; Staib, A.; Sobolewski, A. L.; Domcke, W. Phys. Chem. Chem. Phys. 2000, 2, 4341-4353.
18. Parusel, A. B. J.; Köhler, G.; Grimme, S. J. Phys. Chem. A 1998, 102, 6297-6306.
19. Parusel, A. B. J.; Köhler, G.; Nooijen, M. J. Phys. Chem. A 1999, 103, 4056-4064.
20. Parusel, A. B. J.; Rettig, W.; Sudholt, W. J. Phys. Chem. A 2002, 106, 804-815.
21. Dreyer, J.; Kummrow, A. J. Am. Chem. Soc. 2000, 122, 2577-2585.
22. Cammi, R.; Menucci, B.; Tomasi, J. J. Phys. Chem. A 2000, 104, 5631-5637.
23. Menucci, B.; Toniolo, A.; Tomasi, J. J. Aro. Chem. Soc. 2000, 122, 10621-10630.
24. Zilberg, S.; Haas, Y. J. Phys. Chem. A 2002, 106, 1-11.
25. Jamorski Jödicke, C.; Lüthi, H. P. J. Chem. Phys. 2002, 117, 4146-4167.
26. Rappoport, D.; Furche, F. J. Am. Chem. Soc. 2004, 126, 1277-1284.
27. Hashimoto, M.; Hamaguchi, H. J. Phys. Chem. 1995, 99, 7875-7877.
28. Kwok, W. M.; Ma, C.; Matousek, P.; Parker, A. W.; Phillips, D.; Toner, W. T.; Towrie, M. Chem. Phys. Lett. 2000, 322, 395-400.
29. Kwok, W. M.; Ma, C.; Matousek, P.; Parker, A. W.; Phillips, D.; Toner, W. T.; Towrie, M.; Umapathy, S. J. Phys. Chem. A 2001, 105, 984-990.
30. Okamoto, H.; Inishi, H.; Nakamura, Y.; Kohtani, S.; Nakagaki, R. J. Phys. Chem. A 2001, 105, 4182-4188.
31. Okamoto, H.; Kinoshita, M.; Kohtani, S.; Nakagaki, R.; Zachariasse, K. A. Bull. Chem. Soc. Jpn. 2002, 75, 957-963.
32. Kwok, W. M.; Ma, C.; Phillips, D.; Matousek, P.; Parker, A. W.; Towrie, M. J. Phys. Chem. A 2000, 104, 4188-4197.
33. Ma, C.; Kwok, W. M.; Matousek, P.; Parker, A. W.; Phillips, D.; Toner, W. T.; Towrie, M. J. Phys. Chem. A 2002, 106, 3294-3305.
34. Chudoba, C.; Kummrow, A.; Dreyer, J.; Stenger, J.; Nibbering, E.; Elsaesser, T.; Zachariasse, K. Chem. Phys. Lett. 1999, 309, 357-363.
35. It should be noted, however, that the neglect of correlation effects causes CASSCF force constants (like CIS force constants) to be too high, especially if only very small active spaces are chosen. The authors of ref 21 therefore had to use the usual scaling factor for Hartree-Fock force-constant calculations of 0.9 to obtain results that can be compared to experimental numbers.
36. Tozer, D. J. J. Chem. Phys. 2003, 119, 12697-12699.
37. Christiansen, O.; Koch, H.; Jorgensen, P. Chem. Phys. Lett. 1995, 243, 409-418.
38. Hättig, C. J. Chem. Phys. 2003, 118, 7751-7761.
39. Köhn, A.; Hättig, C. J. Chem. Phys. 2003, 119, 5021-5036.
40. Hättig, C.; Weigend, F. J. Chem. Phys. 2000, 113, 5154-5162.
41. Ahlrichs, R.; Bär, M.; Horn, H.; Kölmel, C. Chem. Phys. Lett. 1989, 162, 165-169.
42. Whitten, J. L. J. Chem. Phys. 1973, 58, 4496-4501.
43. Dunlap, B. I.; Conolly, J. W. D.; Sabin, J. R. J. Chem. Phys. 1979, 71, 3396-3402.
44. Vahtras, O.; Almlöf, J. E.; Feyereisen, M. W. Chem. Phys. Lett. 1993, 213, 514.
45. Hättig, C.; Köhn, A. J. Chem. Phys. 2002, 117, 6939-6951.
46. Schäfer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100 (8), 5829-5835.
47. Weigend, F.; Häser, M.; Patzelt, H.; Ahlrichs, R. Chem. Phys. Lett. 1998, 294, 143-152.
48. Schäfer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97 (4), 2571-2577.
49. Christiansen, O.; Koch, H.; Jorgensen, P. J. Chem. Phys. 1996, 105, 1451-1459.
50. Helgaker, T.; Jensen, H. J. A.; Jørgensen, P.; Olsen, J.; Ruud, K.; Ågren, H.; Auer, A. A.; Bak, K. L.; Bakken, V.; Christiansen, O.; Coriani, S.; Dahle, P.; Dalskov, E. K.; Enevoldsen, T.; Fernandez, B.; Hättig, C.; Hald, K.; Halkier, A.; Heiberg, H.; Hettema, H.; Jonsson, D.; Kirpekar, S.; Kobayashi, R.; Koch, H.; Mikkelsen, K. V.; Norman, P.; Packer, M. J.; Pedersen, T. B.; Ruden, T. A.; Sanchez, A.; Saue, T.; Sauer, S. P. A.; Schimmelpfennig, B.; Sylvester-Hvid, K. O.; Taylor, P. R.; Vahtras, O. Dalton - An electronic structure program, release 1.2; 2001.
51. Heine, A.; Herbst-Irmer, R.; Stalke, D.; Kühnle, W.; Zachariasse, K. A. Acta Crystallogr. 1994, B50, 363-373.
52. Kajimoto, O.; Yokoyama, H.; Ooshima, Y.; Endo, Y. Chem. Phys. Lett. 1991, 179, 455-459.
53. Saigusa, H.; Miyakoshi, N.; Mukai, C.; Fukagawa, T.; Kohtani, S.; Nakagaki, R.; Gordon, R. J. Chem. Phys. 2003, 119, 5414-5422.
54. Lommantzsch, U.; Gerlach, A.; Lahmann, C.; Brutschy, B. J. Phys. Chem. A 1998, 102, 6421-6435.
55. Pérez Salgado, F.; Herbich, J.; Kunst, A. G. M.; Rettschnick, R. P. H. J. Phys. Chem. A 1999, 103, 3184-3192.
56. Okamoto, H. J. Phys. Chem. A 2000, 104, 4182-4187.
57. Wilson, Jr., E. B. Phys. Rev. 1934, 45, 706-714.
58. 6, it is dominated by the stretching mode. In the present work, 19a/b is understood to be the stretching mode.
59. Kwok, W. M.; George, M. W.; Grills, D. C.; Ma, C.; Matousek, P.; Parker, A. W.; Phillips, D.; Toner, W. T.; Towrie, M. Angew. Chem., Int. Ed. 2003, 42, 1826-1830.
60. Christiansen, O.; Stanton, J. F.; Gauss, J. J. Chem. Phys. 1997, 108, 3987-4001.
61. Goodman, L.; Ozkabak, A. G.; Thakur, S. N. J. Phys. Chem. 1991, 95, 9044-9058.
62. This was done for simplicity. In sections 3.3 and 3.4, we will investigate whether further symmetry lowering occurs.
63. Gorse and Pesquer (ref 11) also tried to model solvation effects based on semiempirical AM1 calculations. Their in vacuo results, however, yielding potential energy curves that for both LE and ICT increase strongly as the dimethyl-amino group is twisted, are in conflict with more elaborate ab initio results such as the present work and put serious doubts on the applicability of the AM1 method.
64. Grassian, V. H.; Warren, J. A.; Bernstein, E. R. J. Chem. Phys. 1988, 90, 3994-3999.
65. -1 (ref 33).
66. That vibronically excited states are involved in the ICT emission process has already been discussed in connection with the temperature dependence of the ICT band; see ref 4 and references therein.
67. Fuß, W.; Pushpa, K. K.; Rettig, W.; Schmid, W. E.; Trushin, S. A. Photochem. Photobiol. Sci. 2002, 1, 255-262.
68. Trushin, S. A.; Yatsuhashi, T.; Fuß, W.; Schmid, W. E. Chem. Phys. Lett. 2003, 376, 282-291.
69. In ref 26, it was noted, however, that, for twisted geometries, the Hartree-Fock solution becomes triplet-unstable.
70. 2v-symmetric minimum for the TICT state. From the absolute energy given in the supplement to their article, we conclude that state-averaging was used which may explain the different result. State-averaging, however, is problematic for the ICT state, since the active space is too small to account for the large relaxation effects upon transition from the ground state to the ICT state.
71. 2 state would be expected to be the direct counterpart of the TICT state in DMABN.