Abstract
We review the recent studies of the photoisomerization dynamics of azobenzene and its derivatives by surface hopping simulations based on semiempirical potential energy surfaces. We examine the ability of semiclassical methods to predict the excited state dynamics and to reproduce transient spectroscopic signals that constitute the most direct experimental evidence in this field. We show that the available simulation methods yield a deep insight into the mechanism of photochemical reactions and excited state decay, and a fairly good quantitative agreement with experimental findings. Probably the most important technical improvements we can envisage concern the surface hopping algorithm and the usage of ab initio data in the simulation of transient spectra. Concerning azobenzene, our results show that the isomerization mechanism is torsion of the N=N double bond, both by n → π* and by π → π* excitation. The influence of the solvent and the findings of some recent femtochemistry experiments deserve further work to be fully interpreted.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Ciminelli C, Granucci G, Persico M (2004). Chem Eur J 10:2327
Toniolo A, Ciminelli C, Persico M, Martínez TJ (2005). J Chem Phys 123:234308
Ciminelli C, Granucci G, Persico M (2005). J Chem Phys 123:174317
Ciminelli C, Granucci G, Persico M in preparation
Toniolo A, Thompson AL, Martínez TJ (2004). Chem Phys 304:133
Barbatti M, Granucci G, Persico M, Lischka H (2005). Chem Phys Lett 401:276
Cacelli I, Evangelista F, Granucci G, Persico M, unpublished results
Rau H, Lüddecke E (1982). J Am Chem Soc 104:1616
Rau H (1984). J Photochem 26:221
Rau H, Yu-Quan S (1988). J Photochem Photobiol A 42:321
Rau H (1990) In: Durr H, Bouas-Laurent H, (eds) Photochromism. Molecules and systems Elsevier, Amsterdam, Chapt. 4, p 165
Horspool W (2000) In: Patai S (ed), The Chemistry of the hydrazo, azo and azoxy groups, vol 2, Wiley, New York
Diau EW-G (2004). J Phys Chem A 108:950
Chang C-W, Lu Y-C, Wang T-T, Diau EW-G (2004). J Am Chem Soc 126:10109
Schultz T, Quenneville J, Levine B, Toniolo A, Martínez TJ, Lochbrunner S, Schmitt M, Schaffer JP, Zgierski MZ, Stolow A (2003). J Am Chem Soc.125:8098
Tamai N, Miyasaka H (2000). Chem Rev 100:1875
Lednev IK, Ye T-Q, Hester RE, Moore JN (1996). J Phys Chem 100:13338
Lednev IK, Ye T-Q, Matousek P, Towrie M, Foggi P, Neuwahl FVR, Umapathy S, Hester RE, Moore JN (1998). Chem Phys Lett 290:68
Nägele T, Hoche R, Zinth W, Wachtveitl J (1997). Chem Phys Lett 272:489
Hamm P, Ohline SM, Zinth W (1997). J Chem Phys 106:519
Terazima M, Takezaki M, Yamaguchi S, Hirota N (1998). J Chem Phys 109:603
Fujino T, Tahara T (2000). J Phys Chem A 104:4203
Fujino T, Arzhantsev SYu, Tahara T (2001). J Phys Chem A 105:8123
Lu Y-C, Chang C-W, Diau EW-G (2002). J Chin Chem Soc 49:693
Satzger H, Spörlein S, Root C, Wachtveitl J, Zinth W, Gilch P (2003). Chem Phys Lett 372:216
Satzger H, Root C, Braun M (2004). J Phys Chem A 108:6265
Zimmermann G, Chow L-Y, Paik U-J (1958). J Am Chem Soc 80:3528
Gegiou D, Muszkat KA, Fischer E (1968). J Am Chem Soc 90:12
Ronayette J, Arnaud R, Lebourgeois P, Lemaire J (1974). Can J Chem 52:1848
Bortolus P, Monti S (1979). J Phys Chem 83:648
Gauglitz G, Hubig S (1985). J Photochem 30:121
Siampiringue N, Guyot G, Monti S, Bortolus P (1987). J Photochem 37:185
Jungwirth P, Gerber RB (1999). Chem Rev 99:1583
Beck MH, Jäckle A, Worth GA, Meyer H-D (2000). Phys Rep 324:1
Meyer H-D, Worth GA (2003). Theor Chem Acc 109:251
Markmann A, Worth GA, Mahapatra S, Meyer H-D, Köppel H, Cederbaum LS (2005). J Chem Phys 123:204310
Tully JC (1998). Faraday Discuss 110:407
Topaler MS, Allison TC, Schwenke DW, Truhlar DG (1998). J Chem Phys 109:3321
Drukker K (1999). J Comput Phys 153:225
Bonačić-Koutecký V, Mitrić R (2005). Chem Rev 105:11
Heller EJ (1975). J Chem Phys 62:1544
Ben-Nun M, Quenneville J, Martínez TJ (2000). J Phys Chem A 104:5161
Toniolo A, Olsen S, Manohar L, Martínez TJ (2004). Faraday Discuss. 127:149
Pacher T, Cederbaum LS, Köppel H (1993). Adv Chem Phys 84:293
Persico M (1998) In: Electronic diabatic states: definition, computation and applications. in Encyclopedia of Computational Chemistry; Schleyer PvR, Allinger NL, Clark T, Gasteiger J, Kollman PA, Schaefer III HF, Schreiner PR (Eds) Wiley, Chichester, p 852
Cattaneo P, Persico M (2000). Theoret Chem Acc 103:390
Cattaneo P, Persico M (2001). J Am Chem Soc 123:7638
Vreven T, Bernardi F, Garavelli M, Olivucci M, Robb MA, Schlegel HB (1997). J Am Chem Soc 119:12687
Kaledin AL, Morokuma K (2000). J Chem Phys 113:5750
Barbatti M, Aquino AJA, Lischka H (2006). Mol Phys 104:1053
Barbatti M, Granucci G, Lisckha H, Ruckenbauer M (2006) NEWTON-X, Institute of Theoretical Chemistry, University of Vienna
Clifford S, Bearpark MJ, Bernardi F, Olivucci M, Robb MA, Smith BR (1995). J Am Chem Soc 242:27
Granucci G, Toniolo A (2000). Chem Phys Lett 325:79
Granucci G, Persico M, Toniolo A (2001). J Chem Phys 114:10608
Patchkovskii S, Thiel W (1997). Theoret Chem Acc 98:1
Persico M, Granucci G, Inglese S, Laino T, Toniolo A (2003). J Mol Struct Theochem 621:119
Toniolo A, Ciminelli C, Granucci G, Laino T, Persico M (2004). Theoret Chem Acc 93:270
Case DA, Pearlman DA, Caldwell JW, T.E. Cheatham III Wang J, Ross WS, Simmerling CL, Darden TA, Merz KM, Stanton RV, Cheng AL, Vincent JJ, Crowley M, Tsui V, Gohlke H, Radmer RJ, Duan Y, Pitera J, Massova I, Seibel GL, Singh UC, Weiner PK, Kollman PA (2002) AMBER 7, University of California, San Francisco
Dang LX, Pettitt BM (1987). J Phys Chem 91:3349
Antes I, Thiel W (1999). J Phys Chem A 103:9290
Stewart JJP (2002) MOPAC 2000 and MOPAC 2002. Fujitsu Limited, Tokio, Japan
Tully JC (1990). J Chem Phys 93:1061
Adamson AW, Vogler A, Kunkely H, Wachter R (1978). J Am Chem Soc 100:1298
Monti S, Orlandi G, Palmieri P (1982). Chem Phys 71:87
Cattaneo P, Persico M (1999). PCCP 1:4739
Ishikawa T, Noro T, Shoda T (2001). J Chem Phys 115:7503
Gagliardi L, Orlandi G, Bernardi F, Cembran A, Garavelli M (2004). Theoret Chem Acc 111:363
Cembran A, Bernardi F, Garavelli M, Gagliardi L, Orlandi G (2004). J Am Chem Soc 126:3234
Lu Y-C, Diau EW-G, Rau H (2005). J Phys Chem A 109:2090
Granucci G, Persico M in preparation
Müller U, Stock G (1997). J Chem Phys 107:6230
Jasper AW, Truhlar DG (2003). Chem Phys Lett 369:60
Parandekar PV, Tully JC (2005). J Chem Phys 122:094102
Cusati T, Granucci G, Persico M, Spighi G in preparation
Seideman T (2002). Annu Rev Phys Chem 53:41
Mitrić R, Bonačić-Koutecký V, Pittner J, Lischka H (2006). J Chem Phys 125:024303
Suzuki Y, Stener M, Seideman T (2003). J Chem Phys 118:4432
Vollmer MS, Clark TD, Steinem C, Reza Ghadiri M (1999). Angew Chem Int Ed 38:1598
Qu W, Tan H, Chen G, Liu R (2003). Phys Chem Chem Phys 5:2327
Yager KG, Barrett CJ (2006). J Photochem Photobiol A 182:250
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Granucci, G., Persico, M. Excited state dynamics with the direct trajectory surface hopping method: azobenzene and its derivatives as a case study. Theor Chem Account 117, 1131–1143 (2007). https://doi.org/10.1007/s00214-006-0222-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00214-006-0222-1