Abstract
The vertical electronic spectrum of methylenecyclopropene, the prototype of the nonalternant hydrocarbons known as fulvenes, has been studied using multiconfigurational second-order perturbation theory. The calculations comprise three valence states and the 3s, 3p, and 3d members of the Rydberg series converging to the first π ionization limit. Vertical excitation energies to three valence states are found at 4.13, 6.12, and 6.82 eV. The second of them corresponds to an excitation from the highest occupied σ orbital to a π* orbital, while the other two are π → π* excitations. The third transition gives rise to the most intense feature in the electronic spectrum. The results are rationalized within the scheme of two interacting double bonds. Comparisons are made between this and the previous theoretical calculations of the electronic spectra of related systems and also between the available experimental data of methylenecyclopropene in solution.
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Johnson RP, Schmidt MW (1981) J Am Chem Soc 103:3244
Malrieu JP, Maynau D (1982) J Am Chem Soc 104:3021
Billups WE, Lin L-J, Casserly EW (1984) J Am Chem Soc 106:3698
Staley SW, Norden TD (1984) J Am Chem Soc 106:3699
Hess Jr. BA, Michalska D, Schaad LJ (1985) J Am Chem Soc 107:1449
Michalska D, Hess Jr. BA, Schaad LJ (1986) Int J Quantum Chem 29:1127
Norden TD, Staley SW, Taylor WH, Harmony MD (1986) J Am Chem Soc 108:7912
Staley SW, Norden TD (1989) J Am Chem Soc111:445
Bogey M, Cordonnier M, Destombes J-L, Denis J-M, Guillemin J-C (1991) J Mol Spectr 149:230
Roos BO (1987) The complete active space self-consistent field method and its applications in electronic structure calculations. In: Lawley KP (ed) Advances in chemical physics; ab initio methods in quantum chemistry — II, Chap. 69, Wiley, Chichester, p. 399
Andersson K, Malmqvist P-Å, Roos BO, Sadlej AJ, Wolinski K (1990) J Phys Chem 94:5483
Andersson K, Malmqvist P-Å, Roos BO (1992) J Chem Phys 96:1218
Roos BO, Fülscher MP, Malmqvist P-Å, Merchán M, Serrano-Andrés L (1995) Theoretical studies of electronic spectra of organic molecules. In: Langhoff SR (ed) Quantum mechanical electronic structure calculations with chemical accuracy. Kluwer Academic Publishers, Dordrecht, p. 357
Serrano-Andrés L, Roos BO, Merchán M (1994) Theor Chim Acta 87:387
Serrano-Andrés L, Merchán M, Nebot-Gil I, Roos BO, Fülscher MP (1993) J Am Chem Soc 115:6184
Serrano-Andrés L, Merchán M, Fülscher M, Roos BO (1993) Chem Phys Lett 211:125
Roos BO, Merchán M, McDiarmid R, Xing X (1994) J Am Chem Soc 116:5927
Widmark P-O, Malmqvist P-Å, Roos BO (1990) Theor Chim Acta 77:291
Malmqvist P-Å (1986) Int J Quantum Chem 30:479
Malmqvist P-Å, Roos BO (1989) Chem Phys Lett 155:189
Andersson K, Fülscher MP, Karlström G, Lindh R, Malmqvist P-Å, Olsen J, Roos BO, Sadløj AJ, Blomberg MRA, Siegbahn PEM, Kellö V, Noga J, Urban M, Widmark P-O (1994) MOLCAS Version 3. Dept of Theor Chem., Chem Center, Univ of Lund, P.O.B. 124, S-221 00 Lund, Sweden, Lund
González-Luque R, Merchán M, Roos BO (1996) Z Physik D 36:311
Petrongolo C, Buenker RJ, Peyerimhoff SD (1982) J Chem Phys 76:3655
Lindh R, Roos BO (1989) Int J Quantum Chem 35:813
Serrano-Andrés L, Merchàn M, Nebot-Gil I, Lindh R, Roos BO (1993) J Chem Phys 98:3151
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Merchant, M., González-Luque, R. & Roos, B.O. A theoretical determination of the electronic spectrum of Methylenecyclopropene. Theoret. Chim. Acta 94, 143–154 (1996). https://doi.org/10.1007/BF00191645
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DOI: https://doi.org/10.1007/BF00191645