configurations and results in the occurrence of unphysical mixed-spin states. The
use of ad hoc spin-purification procedures [96] should be discouraged as it destroys
the correct dimensionality of the CI seam [43].
In view of the widespread availability of the LR-TD-DFT method in quantum
chemical codes, we would like to raise concerns about using this method for
investigating the dynamics of excited states. It is our hope that the arguments
presented in this chapter can help researchers in this area to make reasonable
choices when selecting the computational methodology for applications.
References
1. McNaught AD, Wilkinson A (1997) IUPAC. Compendium of chemical terminology, 2nd
edn. (The ”Gold Book”). Blackwell, Oxford
2. Mezey PO (1987) Potential energy hypersurfaces. Elsevier, New York
3. Allinger NL (1976) In: Gold V, Bethell D (eds) Advances in physical organic chemistry, vol
13. Academic, London, pp 1–82
4. Born M, Oppenheimer R (1927) Ann Phys 84:457
5. Baer M (2006) Beyond Born–Oppenheimer: electronic nonadiabatic coupling terms and
conical intersections. Wiley, Hoboken
6. Atchity GJ, Xantheas SS, Ruedenberg K (1991) J Chem Phys 95:1862
7. Domcke W, Yarkony DR, K€ oppel H (eds) (2004) Conical intersections. Electronic structure,
dynamics and spectroscopy. Advanced series in physical chemistry, vol 15. World Scientific,
Singapore
8. Domcke W, Yarkony DR, K€ oppel H (eds) (2011) Conical intersections. Theory, computation
and experiment. Advanced series in physical chemistry, vol. 17 World Scientific, Singapore
9. Yarkony DR (1996) Rev Mod Phys 68:985
10. Bernardi F, Olivucci M, Robb MA (1996) Chem Soc Rev 25:321
11. Yarkony DR (2004) In: Domcke W, Yarkony DR, K€ oppel H (eds) Conical intersections.
electronic structure, dynamics and spectroscopy. Advanced series in physical chemistry, vol
15. World Scientific, Singapore, pp 41–127
12. Migani A, Olivucci M (2004) In: Domcke W, Yarkony DR, K€ oppel H (eds) Conical
intersections. electronic structure, dynamics and spectroscopy. Advanced series in physical
chemistry, vol 15. World Scientific, Singapore, pp 271–320
13. Butler LJ (1998) Annu Rev Phys Chem 49:125
14. Soto J, Arenas JF, Otero JC, Pelez D (2006) J Phys Chem A 110:8221
15. Hund F (1927) Z Phys 40:742
16. von Neumann J, Wigner E (1929) Physik Z 30:467
17. Teller E (1937) J Phys Chem 41:109
18. Herzberg G, Longuet-Higgins HC (1963) Discuss Faraday Soc 35:77
19. Longuet-Higgins HC (1975) Proc R Soc Lond Ser A 344:147
20. Truhlar DG, Mead CA (2003) Phys Rev A 68:032501
21. Polanyi JC (1972) Acc Chem Res 5:161
22. Polanyi JC (1987) Science 236:680
23. Sellner B, Barbatti M, Lischka H (2009) J Chem Phys 131:024312
24. Robb MA (2011) In: Domcke W, Yarkony DR, K€ oppel H (eds) Conical intersections.
Theory, computation and experiment. Advanced series in physical chemistry, vol 17.
World Scientific, Singapore, pp 3–50
Description of Conical Intersections with Density Functional Methods
473
use of ad hoc spin-purification procedures [96] should be discouraged as it destroys
the correct dimensionality of the CI seam [43].
In view of the widespread availability of the LR-TD-DFT method in quantum
chemical codes, we would like to raise concerns about using this method for
investigating the dynamics of excited states. It is our hope that the arguments
presented in this chapter can help researchers in this area to make reasonable
choices when selecting the computational methodology for applications.
References
1. McNaught AD, Wilkinson A (1997) IUPAC. Compendium of chemical terminology, 2nd
edn. (The ”Gold Book”). Blackwell, Oxford
2. Mezey PO (1987) Potential energy hypersurfaces. Elsevier, New York
3. Allinger NL (1976) In: Gold V, Bethell D (eds) Advances in physical organic chemistry, vol
13. Academic, London, pp 1–82
4. Born M, Oppenheimer R (1927) Ann Phys 84:457
5. Baer M (2006) Beyond Born–Oppenheimer: electronic nonadiabatic coupling terms and
conical intersections. Wiley, Hoboken
6. Atchity GJ, Xantheas SS, Ruedenberg K (1991) J Chem Phys 95:1862
7. Domcke W, Yarkony DR, K€ oppel H (eds) (2004) Conical intersections. Electronic structure,
dynamics and spectroscopy. Advanced series in physical chemistry, vol 15. World Scientific,
Singapore
8. Domcke W, Yarkony DR, K€ oppel H (eds) (2011) Conical intersections. Theory, computation
and experiment. Advanced series in physical chemistry, vol. 17 World Scientific, Singapore
9. Yarkony DR (1996) Rev Mod Phys 68:985
10. Bernardi F, Olivucci M, Robb MA (1996) Chem Soc Rev 25:321
11. Yarkony DR (2004) In: Domcke W, Yarkony DR, K€ oppel H (eds) Conical intersections.
electronic structure, dynamics and spectroscopy. Advanced series in physical chemistry, vol
15. World Scientific, Singapore, pp 41–127
12. Migani A, Olivucci M (2004) In: Domcke W, Yarkony DR, K€ oppel H (eds) Conical
intersections. electronic structure, dynamics and spectroscopy. Advanced series in physical
chemistry, vol 15. World Scientific, Singapore, pp 271–320
13. Butler LJ (1998) Annu Rev Phys Chem 49:125
14. Soto J, Arenas JF, Otero JC, Pelez D (2006) J Phys Chem A 110:8221
15. Hund F (1927) Z Phys 40:742
16. von Neumann J, Wigner E (1929) Physik Z 30:467
17. Teller E (1937) J Phys Chem 41:109
18. Herzberg G, Longuet-Higgins HC (1963) Discuss Faraday Soc 35:77
19. Longuet-Higgins HC (1975) Proc R Soc Lond Ser A 344:147
20. Truhlar DG, Mead CA (2003) Phys Rev A 68:032501
21. Polanyi JC (1972) Acc Chem Res 5:161
22. Polanyi JC (1987) Science 236:680
23. Sellner B, Barbatti M, Lischka H (2009) J Chem Phys 131:024312
24. Robb MA (2011) In: Domcke W, Yarkony DR, K€ oppel H (eds) Conical intersections.
Theory, computation and experiment. Advanced series in physical chemistry, vol 17.
World Scientific, Singapore, pp 3–50
Description of Conical Intersections with Density Functional Methods
473