Abstract
A simulation of the \(n\rightarrow\pi^*\) absorption and the \(\pi^*\rightarrow n\) fluorescence of acetone in aqueous solution is reported. The model has an explicit solvent representation with an effective ab initio treatment of the solute. The model attempts to balance quantum chemistry, intermolecular interactions and statistical thermodynamics. It includes a non-electrostatic perturbation on the solute which models the solute–solvent exchange repulsion and the restriction put on the electronic structure of the solute by the antisymmetry to the solvent. The solvent shift to the absorption transition is found to be between 0.16 and 0.21 eV; the shift to the fluorescence transition is found to be between 0.02 and 0.05 eV. The simulation supports the conclusion that the first peak in the fluorescence spectrum of acetone is from a single molecule in equilibrium with the solvent, not from an excimer.
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References
Szabo A, Ostlund NS (1989). Modern quantum chemistry. Introduction to advanced electronic structure theory. Dover Publications, Mineola
Bauschlicher CW, Langhoff SR (1991). Chem Rev 91:701
Roos BO, Andersson K, Fülscher MP, Malmqvist P-Å, Serrano-Anderés L, Pierloot K, Merchán M (1996). Adv Chem Phys 93:219
Serrano-Andrés L, Merchán M (2005). J Mol Struct Theochem 729:99
Öhrn A, Karlström G (2006). Mol Phys (in press)
Öhrn A, Karlström G (2006). J Phys Chem A 110:1934
Reichhardt C (2003). Solvents and solvent effects in organic chemistry, 3rd edn. Wiley, Weinheim
Bayliss NS, McRae EG (1954). J Phys Chem 58:1002
Ågren H, Mikkelsen KV, (1991). J Mol Struct Theochem 234:425
Pimentel GC (1957). J Am Chem Soc 59:3323
Metropolis NA, Rosenbluth W, Rosenbluth MN, Teller AH, Teller E (1953). J Chem Phys 21:1087
Allen MP, Tildesley DJ (1989). Computer simulation of liquids. Oxford University Press, Oxford
Roos BO, Taylor PR, Siegbahn PEM (1980). Chem Phys 48:157
Roos BO (1987). Adv Chem Phys 69:399
Roos BO, Andersson K, Fülscher MP (1992). Chem Phys Lett 192:5
Malmqvist P-Å (1986). Int J Quantum Chem 30:479
Malmqvist P-Å, Roos BO (1989). Chem Phys Lett 155:189
Wallqvist A, Ahlström P, Karlström G (1990). J Phys Chem 94:1649
Li J, Cramer CJ, Truhlar DG (2000). Int J Quantum Chem 77:264
Longuet-Higgins HC, Pople JA (1957). J Chem Phys 27:192
Rösch N, Zerner MC (1994). J. Phys. Chem. 98:5817
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
Pierloot K, Dumez B, Widmark P-O, Roos BO (1995). Theor Chim Acta 90:87
Stålring J, Bernhardsson A, Lindh R (2001). Mol Phys 99:103
Laane J, (1999). In: Laane J, Takahashi H, Bandrauk AD (eds). Structure and dynamics of electronic excited states. Springer,Berlin Heidelberg New York, p 3
Angeli C, Borini A, Ferrighi L, Cimiraglia R (2005). J Mol Struct Theochem 718:55
Walsh AD, (1953). J Chem Soc 2306
Boys SF, Bernardi F (1970). Mol Phys 19:553
Moriarty NW, Karlström G (1996). J Phys Chem 100:17791
Karlström G, Lindh R, Malmqvist P-Å, Roos BO, Ryde U, Veryazov V, Widmark P-O, Cossi M, Schimmelpfennig B, Neogrady P, Seijo L (2003). Comput Mater Sci 28:222
Bayliss NS, McRae EG (1954). J Phys Chem 58:1006
Balasubramanian A, Rao CNR (1962). Spectrochim Acta 18:1337
Bernasconi L, Sprik M, Hütter J (2003). J Chem Phys 119:12417
Ten-no S, Hirata F, Kato S (1994). J Chem Phys 100: 7443
Thompson MA (1996). J Phys Chem 100:14492
De Vries AH, van Duijnen PTh (1996). Int J Quantum Chem 57:1067
Serrano-Andrés L, Fülscher MP, Karlström G (1997). Int J Quantum Chem 65:167
Martín ME, Sánchez ML, Olivares del Valle FJ, Aguilar MA (2000). J Chem Phys 113:6308
Coutinho K, Canuto S (2003). J Mol Struct Theochem 632:235
Aquilante F, Cossi M, Crescenzi O, Scalmani G, Barone V (2003). Mol Phys 101:1945
Röhrig UF, Frank I, Hutter J, Laio A, VandeVondele J, Rothlisberger U (2003). ChemPhysChem 4:1177
Aidas K, Kongsted J, Osted A, Mikkelsen KV, Christiansen O (2005). J Phys Chem A 109:8001
Crescenzi O, Pavone M, De Angelis F, Barone V (2005). J Phys Chem B 109:445
Neugebauer J, Louwerse MJ, Baerends EJ, Wesolowski TA (2005). J Chem Phys 122:094115
Borkman RF, Kearns DR (1966). J Chem Phys 44:945
O’Sullivan M, Testa AC (1968). J Am Chem Soc 90:6245
Renkes GD, Wettack FS (1969). J Am Chem Soc 91:7514
Wettack FS (1969). J Phys Chem 73:1167
O’Sullivan M, Testa AC (1970). J Am Chem Soc 92:5842
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Öhrn, A., Karlström, G. Hybrid Monte Carlo simulations of vertical electronic transitions in acetone in aqueous solution. Theor Chem Acc 117, 441–449 (2007). https://doi.org/10.1007/s00214-006-0172-7
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DOI: https://doi.org/10.1007/s00214-006-0172-7