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Single determinant calculations of excited state polarizabilities
1997 (English)In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 224, no 2-3, 201-214 p.Article in journal (Refereed) Published
Abstract [en]

We apply response theory to simulate excited state polarizabilities emphasizing the possibility to do so by means of optimization of a ground state single determinant only. The excited state polarizabilities are given by the double residues of the cubic response functions. A set of molecules with varying ground state configurations and properties have been considered: water, ozone, formaldehyde, ethylene, butadiene, cyclobutadiene, pyridine, pyrazine and s-tetrazine. The results have been compared to excited state experiments where available and with linear response calculations of the multi-determinant optimized excited state. It is shown that calculations of excited state polarizabilities based on a ground state optimized single determinant work well for most of the cases investigated. This contention is exemplified by the fact that the gas phase value from an electrochromism experiment for the polarizability of the 11B2 excited state of formaldehyde is better reproduced by ground state cubic response theory than by the corresponding separate state linear response function calculation, and by that the calculations call for an experimental reinvestigation of the excited state polarizabilities of s-tetrazine. A few prerequisites are given: The excited state should be isolated in energy, the ordering of the main contributing states should be reproduced, and the geometric conformation of the excited state in question should not be very different from the ground state geometry. The computational and formal advantages of the approach are discussed. © 1997 Elsevier Science B.V.

Place, publisher, year, edition, pages
1997. Vol. 224, no 2-3, 201-214 p.
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-198839ScopusID: 2-s2.0-0031318685OAI: oai:DiVA.org:kth-198839DiVA: diva2:1058701
Note

References: Morales, R.G.E., (1982) J. Phys. Chem., 86, p. 2550; Ghoneim, N., Suppan, P., (1990) J. Chem. Soc. Faraday Trans., 86, p. 2079; Chongwain, P.T., Iweibo, I., (1991) Spectrochimica Acta A, 47, p. 713; Iwebo, I., Chongwain, P.T., Obi-Egbedi, N.O., Lesi, A.F., (1991) Spectrochimica Acta A, 47, p. 705; Sinha, H.K., Thomson, P.C.P., Yates, K., (1990) Can. J. Chem., 68, p. 1507; Heitz, S., Weidauer, D., Hese, A., (1991) Chem. Phys. Lett., 176, p. 55; Heitz, S., Weidauer, D., Hese, A., (1991) J. Chem. Phys., 95, p. 7952; Heitz, S., Weidauer, D., Rosenow, B., Hese, A., (1992) J. Chem. Phys., 96, p. 976; Rodenberger, D.C., Heflin, J.R., Garito, A.F., (1992) Nature, 359, p. 309; Rodenberger, D.C., Heflin, J.R., Garito, A.F., (1995) Phys. Rev. A, 51, p. 3234; Urban, M., Sadlej, A.J., (1990) Theor. Chim. Acta, 78, p. 189; Foresman, J.B., Head-Gordon, M., Pople, J.A., Frisch, M.J., (1992) J. Phys. Chem., 96, p. 135; Ortiz, J.V., (1994) J. Chem. Phys., 101, p. 6743; Stanton, J.F., Gauss, J., Ishikawa, N., Head-Gordon, M., (1995) J. Chem. Phys., 103, p. 4160; Olsen, J., Jørgensen, P., (1985) J. Chem. Phys., 82, p. 3235; Jonsson, D., Norman, P., Ågren, H., (1996) J. Chem. Phys., 105, p. 6401; Norman, P., Jonsson, D., Ågren, H., (1997) Chem. Phys. Lett., 268, p. 337; Luo, Y., Norman, P., Jonsson, D., Ågren, H., (1996) Mol. Phys., 89, p. 1409; Norman, P., Jonsson, D., Vahtras, O., Ågren, H., (1996) Chem. Phys., 203, p. 23; Norman, P., Jonsson, D., Ågren, H., Dahle, P., Ruud, K., Helgaker, T., Koch, H., (1996) Chem. Phys. Lett., 253, p. 1; Jonsson, D., Norman, P., Luo, Y., Ågren, H., (1996) J. Chem. Phys., 105, p. 581; Helgaker, T., Jensen, H.J.Aa., Jørgensen, P., Olsen, J., Ruud, K., Ågren, H., Andersen, T., Vahtras, O., (1997) Dalton, an Ab Initio Electronic Structure Program. Release 1.0, , http://www.kjemi.uio.no/software/dalton/dalton.html; (1995) Landolt-Börnstein, New Series, 11-23. , Springer Verlag; Widmark, P.-O., Malmqvist, P.-Å., Roos, B.O., (1990) Theor. Chim. Acta, 77, p. 291; Widmark, P.-O., Persson, B.J., Roos, B.O., (1991) Theor. Chim. Acta, 79, p. 419; Sadlej, A.J., (1988) Coll. Chem. Commun., 53, p. 1995; Luo, Y., Ågren, H., Vahtras, O., Jorgensen, P., Spirko, V., Hettema, H., (1993) J. Chem. Phys., 98, p. 7159; John, J.G., Bacskay, G.B., Hush, N.S., (1980) Chem. Phys., 51, p. 49; Andersson, K., Borowski, P., Fowler, P.W., Malmqvist, P.Å., Roos, B.O., Sadlej, A.J., (1992) Chem. Phys. Lett., 190, p. 367; Maroulis, G., (1994) J. Chem. Phys., 101, p. 4949; Nordfors, D., Ågren, H., Jensen, H.J.Aa., (1991) Int. J. Quant. Chem., 40, p. 475; Sadlej, A.J., (1991) Theor. Chim. Acta, 79, p. 123; Hurdis, E.C., Smyth, C.P., (1943) J.am. Chem. Soc., 65, p. 89; Causley, G.C., Russell, B.R., (1978) J. Chem. Phys., 68, p. 3797; Norman, P., Luo, Y., Jonsson, D., Ågren, H., (1997) J. Chem. Phys., 106, p. 1827; Merer, A.J., Mulliken, R.S., (1969) Chem. Rev., 69, p. 639; CRC, Boca Raton, 1985Chen, Y.T., Oka, T., (1988) J. Chem. Phys., 88, p. 5282; Salem, L., (1982) Electrons in Chemical Reactions: First Principles, , Wiley; Balková, A., Bartlett, R.J., (1994) J. Chem. Phys., 101, p. 8972; Archibong, E.F., Thakkar, A.J., (1994) Mol. Phys., 81, p. 557; Okruss, M., Penn, F., Hese, A., (1995) J. Mol. Struct., 348, p. 119; Knuts, S., Vahtras, O., Ågren, H., (1993) J. Mol. Struct. (TEOCHEM), 279, p. 249; Schütz, M., Hutter, J., Lüthi, H.P., (1995) J. Chem. Phys., 103, p. 7048; Werner, H.J., Meyer, W., (1976) Mol. Phys, 31, p. 855; Robin, M.B., (1974) Higher Excited States of Polyatomic Molecules, , Academic Press, New York; Bell, S., (1965) J. Mol. Spectroscopy, 16, p. 205; Mack, K.M., Muenter, J.S., (1977) J. Chem. Phys., 66, p. 5278; Serano-Andrés, L., Merchán, M., Nebot-Gil, I., Lindh, R., Roos, B.O., (1993) J. Chem. Phys., 98, p. 3151. QCR 20170112

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