abstract
One frequently used quantum chemical approach for studies of spectroscopy and photochemistry is the Complete Active Space (CAS) SCF method in combination with multiconfigurational second order perturbation theory (CASPT2). In this chapter we shall describe these two approaches. The basic idea behind them is the request that the wave function should give a proper description of the electronic structure already at the lowest level of theory. This should be possible for all possible arrangements of the electrons: in chemical bonds, in excited states, in dissociated states, at transition states for chemical reactions, etc. It should also be possible for all atoms of the periodic systems. The CASSCF wave function fulfills, in principle, this requirement because it is full CI, albeit in a limited space of active orbitals. CASSCF can therefore be regarded as an extension of the Hartree-Fock (HF) method to any arrangement of the electrons. The addition of dynamic electron correlation is as crucial here as it is in the HF method. The suggested solution is to compute this energy using second order perturbation theory (CASPT2) because it is relatively simple and allows applications to a wide variety of systems and many electrons. The review will focus on the methods themselves. Applications will be described in other chapters of the book
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Roos BO, Taylor PR, Siegbahn PEM (1980) Chem Phys 48: 157.
Roos BO (1987) Advances in Chemical Physics: Ab Initio Methods in Quantum Chemistry - II. In: Lawley KP (ed). John Wiley & Sons Ltd.: Chichester, England, Chapter 69, p. 399.
Andersson K, Malmqvist P-Å, Roos BO, Sadlej AJ, Wolinski K (1990) J Phys Chem 94: 5483–5488.
Andersson K, Malmqvist P-Å, Roos BO (1992) J Chem Phys 96: 1218–1226.
Löwdin P-O (1955) Phys Rev 97: 1474–1520.
Levy B, Berthier G (1968) Int J Quantum Chem 2: 307.
Levy B, Berthier G (1969) Int J Quantum Chem 3: 247.
Ruedenberg K, Sundberg KR (1976) Quantum Science. Methods and Structure. In: Calais J-L (ed). Plenum Press: New York.
Shavitt I (1977) Int J Quantum Chem: Quantum Chem Symp 11: 133.
Shavitt I (1978) Int J Quantum Chem: Quantum Chem Symp 12: 5.
Roothaan CCJ (1960) Revs Mod Phys 32: 179.
Grein F, Chang TC (1971) Chem Phys Lett 12: 44.
Hinze J (1973) J Chem Phys 59: 6424.
Dalgaard E, Jørgensen P (1978) J Chem Phys 69: 3833.
Malmqvist P-Å, Rendell A, Roos BO (1990) J Phys Chem 94: 5477–5482.
Malmqvist P-Å (1986) Int J Quantum Chem 30: 479.
Malmqvist P-Å, Roos BO (1989) Chem Phys Lett 155: 189–194.
Karlström G, Carlsson A, Lindman B (1990) J Phys Chem 94: 5005.
Malmqvist P-Å, Roos BO, Schimmelpfennig B (2002) Chem Phys Lett 357: 230–240.
Siegbahn PEM (1980) J Chem Phys 72: 1647.
Lischka H, Shepard R, Shavitt I, Pitzer RM, Dallos M, Müller T, Szalay PG, Brown FB, Ahlrichs R, Böhm HJ, Chang A, Comeau DC, Gdanitz R, Dachsel H, Ehrhardt C, Ernzerhof M, Höchtl P, Irle S, Kedziora G, Kovar T, Parasuk V, Pepper MJM, Scharf P, Schiffer H, Schindler M, Schüler M, Seth M, Stahlberg EA, Zhao J-G, Yabushita S, Zhang Z COLUMBUS, an ab initio electronic structure program, release 5.9, 2004.
Møller C, Plesset MS (1934) Phys Rev 46: 618–622.
Roos BO, Linse P, Siegbahn PEM, Blomberg MRA (1982) Chem Phys 66: 197.
Olsen J, Roos BO, Jørgensen P, Jensen HJA (1988) J Chem Phys 89: 2185–2192.
Roos BO (2000) European Summer School in Quantum Chemistry, Book II. In Roos BO, Widmark P-O (eds). Lund University: Lund, Sweden.
Roos BO (1980) Int J Quantum Chem S14: 175.
Wong MW, Steudel R (2005) Chem Commun 3712.
Azizi Z, Roos BO, Veryazov V (2006) Phys Chem Chem Phys 8: 2727–2732.
Roos BO, Fülscher MP, Malmqvist P-Å, Merchán M, Serrano-Andrés L (1995) Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy. In: Langhoff SR (ed). Kluwer Academic Publishers: Understanding Chem, React., Dordrecht, The Netherlands pp. 357–438.
Roos BO, Fülscher MP, Malmqvist P-Å, Merchán M, Serrano-Andrés L (1995) Underst Chem React 13: 357.
Roos BO, Andersson K, Fülscher MP, Malmqvist P-Å, Serrano-Andrés L, Pierloot K, Merchán M (1996) Advances in Chemical Physics: New Methods in Computational Quantum Mechanics, Vol. XCIII:219–331. In: Prigogine I, Rice SA, (eds). John Wiley & Sons: New York, pp. 219–332.
Roos BO (2003) Collect Czech Chem Commun 68: 265.
Pierloot K (2004) Mol Phys 101: 2083.
Pierloot K (2004) Computational Photochemistry. In: Michl J, Olivucci M (eds). Elsevier: Amsterdam.
Pierloot K (2001) Computational Organometallic Chemistry. In: Cundari T, (ed). Marcel Decker Inc: New York, P. 123.
Gagliardi L, Roos BO (2005) Nature 433: 848–851.
Roos BO, Malmqvist P-Å, Gagliardi L (2006) J Am Chem Soc 128: 17000–17006.
Gagliardi L, Heaven MC, Krogh JW, Roos BO (2005) J Am Chem Soc 127: 86–91.
Hagberg D, Karlström G, Roos BO, Gagliardi L (2005) J Am Chem Soc 127.
Gagliardi L, Roos BO (2000) Chem Phys Lett 331: 229–234.
Privalov T, Macak P, Schimmelpfennig B, Fromager E, Wahlgren IGU (2004) J Am Chem Soc 126: 9801.
Paulovic J, Gagliardi L, Dyke JM, Hirao K (2004) J Chem Phys 120: 9998–10001.
Karlström G, Malmqvist P-Å (1992) J Chem Phys 96: 6115.
Roos BO, Malmqvist P-Å (2004) Phys Chem Chem Phys 6: 2919–2927.
Andersson K, Roos BO (1993) Int J Quantum Chem 45: 591–607.
Ghigo G, Roos BO, Malmqvist P-Å (2004) Chem Phys Lett 396: 142–149.
Roos BO, Andersson K (1995) Chem Phys Lett 245: 215–223.
Roos BO, Andersson K, Fülscher MP, Serrano-Andrés L, Pierloot K, Merchán M, Molina V (1996) J Mol Struct (Theochem) 388: 257–276.
Forsberg N, Malmqvist P-Å (1997) Chem Phys Lett 274: 196.
Ghigo G, Roos BO, Stancil PC, Weck PF (2004) J Chem Phys 121: 8194–8200.
Finley J, Malmqvist P-Å, Roos BO, Serrano-Andrés L (1998) Chem Phys Lett 288: 299–306.
Merchán M, Serrano-Andrés L (2005) Computational Photochemistry. In: Olivucci M, Michl J (eds). Elsevier: Amsterdam.
Persson BJ, Roos BO, Pierloot K (1994) J Chem Phys 101: 6810.
Pierloot K, Persson BJ, Roos BO (1995) J Phys Chem 99: 3465–3472.
Ryde U, Olsson MHM, Pierloot K, Roos BO (1996) J Mol Biol 261: 586–596.
Pierloot K, De Kerpel JOA, Ryde U, Roos BO (1997) J Am Chem Soc 119: 218–226.
Pierloot K, De Kerpel JOA, Olsson MHM, Ryde U, Roos BO (1997) J Inorg Biochem 67: 43.
Pierloot K, De Kerpel JOA, Ryde U, Olsson MHM, Roos BO (1998) J Am Chem Soc 120: 13156–13166.
Cramer CJ, Kinal A, Woch M, Piecuch P, Gagliardi L (2006) J Phys Chem A 110: 11557–11568.
Roos BO, Borin AC, Gagliardi L (2006) Angew Chem Int Ed 46: 1469–1472.
Brynda M, Gagliardi L, Widmark P-O, Power PP, Roos BO (2006) Angew Chem Int Ed 45: 3888–3891.
La Macchia G, Brynda M, Gagliardi L (2006) Angew Chem Int Ed 45: 6210–6213.
Gagliardi L, Roos BO (2006) Chem Soc Rev DOI: 10.1039/b601115m, xxxx.
Roos BO, Andersson K, Fülscher MP (1992) Chem Phys Lett 192: 5–13.
Goeppert-Mayer M, Sklar AL (1938) J Chem Phys 6: 645.
Bernhardsson A, Forsberg N, Malmqvist P-Å, Roos BO, Serrano-Andrés L (2000) J Chem Phys 112: 2798–2809.
Roos BO, Serrano-Andrés L, Merchán M (1993) Pure & Appl Chem 65: 1693–1698.
De Vico L, Wisborg-Krogh J, Liu Y-J, Lindh R (2007) J Am Chem Soc submitted.
Roos BO (2005) Computational Photochemistry. In: Olivucci M, Michl J (eds). Elsevier: Amsterdam.
Grimme S, Waletzke M (1999) J Chem Phys 111: 5645.
Roos BO, Lindh R, Malmqvist P-Å, Veryazov V, Widmark P-O J Phys Chem A 108: 2851.
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Roos, B.O. (2008). Multiconfigurational quantum chemistry for ground and excited states. In: Shukla, M.K., Leszczynski, J. (eds) Radiation Induced Molecular Phenomena in Nucleic Acids. Challenges and Advances In Computational Chemistry and Physics, vol 5. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8184-2_5
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