single-site energies and electron coupling terms, absorption-band widths could
directly give excited-state lifetimes. To bridge the gap between experiments in
vacuo and in solution, work on partially-hydrated ions is needed. Gradually building up the solvation environment by the attachment of one water molecule at a time
would establish how many water molecules are needed to obtain the absorption of
DNA in bulk solution. In conclusion, there is much more to be done in the future
relating to mass spectrometry and UV spectroscopy of isolated DNA and RNA
nucleotides.
References
1. Crespo-Hernandez, C.E., Cohen, B., Hare, P.M., Kohler, B.: Ultrafast excited-state dynamics
in nucleic acids. Chem. Rev. 104, 1977–2019 (2004)
2. Middleton, C.T., de La Harpe, K., Su, C., Law, Y.K., Crespo-Hernandez, C.E., Kohler, B.:
DNA excited-state dynamics: from single bases to the double helix. Annu. Rev. Phys. Chem.
60, 217–239 (2009)
3. Clark, L.B.: Transition moments of 2
0 -deoxyadenosine. J. Phys. Chem. 99, 4466–4470 (1995)
4. Matsuoka, Y., Norde ´n, B.: Linear dichroism studies of nucleic-acid bases in stretched
polyvinyl-alcohol film - molecular-orientation and electronic-transition moment directions.
J. Phys. Chem. 86, 1378–1386 (1982)
5. Petke, J.D., Maggiora, G.M., Christoffersen, R.E.: Ab initio configuration-interaction and
random phase approximation calculations of the excited singlet and triplet-states of adenine
and guanine. J. Am. Chem. Soc. 112, 5452–5460 (1990)
6. Domcke, W., Yarkony, D.R., Ko ¨ppel, H.: Conical Intersections: Electronic Structure, Dynamics & Spectroscopy. In: Ng, C.-Y. (ed.) Advanced Series in Physical Chemistry, vol. 15. World
Scientific, Singapore (2004)
7. Longworth, J.W., Rahn, R.O., Shulman, R.G.: Luminescence of pyrimidines purines
nucleosides and nucleotides at 77 degrees K. Effect of ionization and tautomerization.
J. Chem. Phys. 45, 2930–2939 (1966)
8. Markovitsi, D., Gustavsson, T., Banyasz, A.: Absorption of UV radiation by DNA: spatial and
temporal features. Mutat. Res. Rev. Mutat. 704, 21–28 (2010)
9. Markovitsi, D., Gustavsson, T., Vaya, I.: Fluorescence of DNA duplexes: from model helices
to natural DNA. J. Phys. Chem. Lett. 1, 3271–3276 (2010)
10. Vaya, I., Gustavsson, T., Miannay, F.A., Douki, T., Markovitsi, D.: Fluorescence of natural
DNA: from the femtosecond to the nanosecond time scales. J. Am. Chem. Soc. 132,
11834–11835 (2010)
11. Nielsen, L.M., Hoffmann, S.V., Nielsen, S.B.: Electronic coupling between photo-excited
stacked bases in DNA and RNA strands with emphasis on the bright states initially populated.
Photochem. Photobiol. Sci. 12, 1273–1285 (2013)
12. Ghosh, D., Isayev, O., Slipchenko, L.V., Krylov, A.I.: Effect of solvation on the vertical
ionization energy of thymine: from microhydration to bulk. J. Phys. Chem. A 115, 6028–6038
(2011)
13. Ghosh, D., Kosenkov, D., Vanovschi, V., Williams, C.F., Herbert, J.M., Gordon, M.S.,
Schmidt, M.W., Slipchenko, L.V., Krylov, A.I.: Noncovalent interactions in extended systems
described by the effective fragment potential method: theory and application to nucleobase
oligomers. J. Phys. Chem. A 114, 12739–12754 (2010)
14. Bravaya, K.B., Kostko, O., Ahmed, M., Krylov, A.I.: The effect of π-stacking, H-bonding, and
electrostatic interactions on the ionization energies of nucleic acid bases: adenine-adenine,
thymine-thymine and adenine-thymine dimers. Phys. Chem. Chem. Phys. 12, 2292–2307
(2010)
10 UV Photophysics of DNA and RNA Nucleotides In Vacuo: Dissociation. . .
203
directly give excited-state lifetimes. To bridge the gap between experiments in
vacuo and in solution, work on partially-hydrated ions is needed. Gradually building up the solvation environment by the attachment of one water molecule at a time
would establish how many water molecules are needed to obtain the absorption of
DNA in bulk solution. In conclusion, there is much more to be done in the future
relating to mass spectrometry and UV spectroscopy of isolated DNA and RNA
nucleotides.
References
1. Crespo-Hernandez, C.E., Cohen, B., Hare, P.M., Kohler, B.: Ultrafast excited-state dynamics
in nucleic acids. Chem. Rev. 104, 1977–2019 (2004)
2. Middleton, C.T., de La Harpe, K., Su, C., Law, Y.K., Crespo-Hernandez, C.E., Kohler, B.:
DNA excited-state dynamics: from single bases to the double helix. Annu. Rev. Phys. Chem.
60, 217–239 (2009)
3. Clark, L.B.: Transition moments of 2
0 -deoxyadenosine. J. Phys. Chem. 99, 4466–4470 (1995)
4. Matsuoka, Y., Norde ´n, B.: Linear dichroism studies of nucleic-acid bases in stretched
polyvinyl-alcohol film - molecular-orientation and electronic-transition moment directions.
J. Phys. Chem. 86, 1378–1386 (1982)
5. Petke, J.D., Maggiora, G.M., Christoffersen, R.E.: Ab initio configuration-interaction and
random phase approximation calculations of the excited singlet and triplet-states of adenine
and guanine. J. Am. Chem. Soc. 112, 5452–5460 (1990)
6. Domcke, W., Yarkony, D.R., Ko ¨ppel, H.: Conical Intersections: Electronic Structure, Dynamics & Spectroscopy. In: Ng, C.-Y. (ed.) Advanced Series in Physical Chemistry, vol. 15. World
Scientific, Singapore (2004)
7. Longworth, J.W., Rahn, R.O., Shulman, R.G.: Luminescence of pyrimidines purines
nucleosides and nucleotides at 77 degrees K. Effect of ionization and tautomerization.
J. Chem. Phys. 45, 2930–2939 (1966)
8. Markovitsi, D., Gustavsson, T., Banyasz, A.: Absorption of UV radiation by DNA: spatial and
temporal features. Mutat. Res. Rev. Mutat. 704, 21–28 (2010)
9. Markovitsi, D., Gustavsson, T., Vaya, I.: Fluorescence of DNA duplexes: from model helices
to natural DNA. J. Phys. Chem. Lett. 1, 3271–3276 (2010)
10. Vaya, I., Gustavsson, T., Miannay, F.A., Douki, T., Markovitsi, D.: Fluorescence of natural
DNA: from the femtosecond to the nanosecond time scales. J. Am. Chem. Soc. 132,
11834–11835 (2010)
11. Nielsen, L.M., Hoffmann, S.V., Nielsen, S.B.: Electronic coupling between photo-excited
stacked bases in DNA and RNA strands with emphasis on the bright states initially populated.
Photochem. Photobiol. Sci. 12, 1273–1285 (2013)
12. Ghosh, D., Isayev, O., Slipchenko, L.V., Krylov, A.I.: Effect of solvation on the vertical
ionization energy of thymine: from microhydration to bulk. J. Phys. Chem. A 115, 6028–6038
(2011)
13. Ghosh, D., Kosenkov, D., Vanovschi, V., Williams, C.F., Herbert, J.M., Gordon, M.S.,
Schmidt, M.W., Slipchenko, L.V., Krylov, A.I.: Noncovalent interactions in extended systems
described by the effective fragment potential method: theory and application to nucleobase
oligomers. J. Phys. Chem. A 114, 12739–12754 (2010)
14. Bravaya, K.B., Kostko, O., Ahmed, M., Krylov, A.I.: The effect of π-stacking, H-bonding, and
electrostatic interactions on the ionization energies of nucleic acid bases: adenine-adenine,
thymine-thymine and adenine-thymine dimers. Phys. Chem. Chem. Phys. 12, 2292–2307
(2010)
10 UV Photophysics of DNA and RNA Nucleotides In Vacuo: Dissociation. . .
203