Abstract
Multireference configuration interaction calculations have been performed on the excited state energy surfaces of the methyleneimmonium cation using recently developed methods for the computation of analytic gradients and nonadiabatic coupling terms. Excited-state structures and minima on the crossing seam have been determined. It was found that the topology of the methyleneimmonium surfaces is qualitatively different from that of the isoelectronic ethylene. In the former case a conical intersection between the S1 and ground states is found for the twisting motion around the CN bond, whereas a more complicated motion including pyramidalization and hydrogen-transfer is needed in case of ethylene.
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Lischka, H., Dallos, M., Shepard, R.: Analytic MRCI Gradient for Excited States: Formalism and Application to the n-π* Valence- and n-(3s,3p) Rydberg States of Formaldehyde. Mol. Phys. 100, 1647–1658 (2002)
Lischka, H., Dallos, M., Szalay, P.G., Yarkony, D.R., Shepard, R.: Analytic Evaluation of Nonadiabatic Coupling Terms at the MR-CI level. I: Formalism. J. Chem. Phys. 120, 7322–7329 (2004)
Dallos, M., Lischka, H., Shepard, R., Yarkony, D.R., Szalay, P.G.: Analytic Evaluation of Nonadiabatic Coupling Terms at the MR-CI level. II. Minima on the Crossing Seam: Formaldehyde and the Photodimerization of Ethylene. J. Chem. Phys. 120, 7330–7339 (2004)
Lischka, H., Shepard, R., Pitzer, R.M., Shavitt, I., Dallos, M., Müller, T., Szalay, P.G., Seth, M., Kedziora, G.S., Yabushita, S., Zhang, Z.: New High-level Multireference Methods in the Quantum-Chemistry Program System COLUMBUS: Analytic MR-CISD and MRAQCC Gradients and MR-AQCC-LRT for Excited States, GUGA Spin-Orbit CI, and Parallel CI Density. Phys. Chem. Chem. Phys. 3, 664–673 (2001)
Lischka, H., Shepard, R., Shavitt, I., Pitzer, R.M., Dallos, M., Müller, T., Szalay, P.G., Brown, F. B., Ahlrichs, R., Böhm, H. J., Chang, A., Comeau, D. C., Gdanitz, R., Dachsel, H., Erhard, C., Ernzerhof, M., Höchtl, P., Irle, S., Kedziora, G., Kovar, T., Parasuk, V., Pepper, M., Scharf, P., Schiffer, H., Schindler, M., Schüler, M., Zhao, J.-G.: COLUMBUS. An Ab Initio Electronic Structure Program, release 5.9 (2004)
Lischka, H., Ventura, E., Dallos, M.: The Diels-Alder Reaction of Ethylene and 1,3-Butadiene: An Extended Multireference Ab Initio Investigation on Structures and Energies of the Concerted and Nonconcerted Pathways. Chem. Phys. Chem. 5, 1365–1371 (2004)
Antol, I., Eckert-Maksić, M., Lischka, H., Maksić, Z.B.: On the Bond-Stretch Isomerism in the Benzo[1,2:4,5]dicyclobutadiene System - An Ab Initio MR-AQCC Study. Chem. Phys. Chem. 5, 975–981 (2004)
Müller, T., Dallos, M., Lischka, H.: The Ethylene 11B1u V State Revisited. J. Chem. Phys. 110, 7176–7184 (1999)
Dallos, M., Müller, T., Lischka, H., Shepard, R.: Geometry Optimization of Excited Valence States of Formaldehyde Using Analytical MR-CISD and MR-AQCC Gradients, and the conical intersection formed by the 11B1(σ-n*) and 21A1(π-π*) states. J. Chem. Phys. 114, 746–757 (2001)
Müller, T., Lischka, H.: Simultaneous Calculation of Rydberg and Valence States: Excited States of Formaldehyde. Theor. Chem. Acc. 106, 369–378 (2001)
Barbatti, M., Paier, J., Lischka, H.: Photochemistry of Ethylene: A Multireference Configuration Interaction Investigation of the Excited-state Energy Surface. J. Chem. Phys. 121, 11614–11624 (2004)
Tully, J.C.: Molecular Dynamics with Electronic Transitions. J. Chem. Phys. 93, 1061–1071 (1990)
Granucci, G., Persico, M., Toniolo, A.: Direct Semiclassical Simulation of Photochemical Processes with Semiempirical Wave Functions. J. Chem. Phys. 114, 10608–10615 (2001)
Barbatti, M., Granucci, G., Persico, M., Lischka, H.: Semiempirical Molecular Dynamics Investigation of the Excited State lifetime of Ethylene. Chem. Phys. Lett. 401, 276–281 (2005)
Pitonak, M., Lischka, H.: Excited-State Potential Energy Surfaces of Silaethylene: a MRCI Investigation. Mol. Phys. (in press)
Barbatti, M., Aquino, A.J.A., Lischka, H.: A Multireference Configuration Interaction Investigation of the Excited-State Energy Surfaces of Fluoroethylene (in Preparation)
Bonačić-Koutecý, V., Schöffel, K., Michls, J.: Critically Heterosymmetric Biradicaloid Geometries of Protonated Schiff Bases. Theor. Chim. Acta. 72, 459–474 (1987)
Bruna, P.J., Peyerimhoff, S.D., Buenker, R.J.: The Ground State of the CN + ion: a Multi-reference CI Study. Chem. Phys. Lett. 72, 278–284 (1981)
Dunning Jr., T.H.: Gaussian Basis Sets for Use in Correlated Molecular Calculations. I. The Atoms Boron through Neon and Hydrogen. J. Chem. Phys. 90, 1007–1023 (1989)
Kendall, R.A., Dunning Jr., T.H.: Electron Affinities of the First-row Atoms Revisited. Systematic Basis Sets and Wave Functions. J. Chem. Phys. 96, 6796–6806 (1992)
van Mourik, T., Wilson, A.K., Dunning Jr., T.H.: Benchmark Calculations with Correlated Molecular Wavefunctions. XIII. Potential Energy Curves for He2, Ne2 and Ar2 using Correlation Consistent Basis Sets through Augmented Sextuple Zeta. Mol. Phys. 96, 529–547 (1999)
Ohmine, I.: Mechanisms of Nonadiabatic Transitions in Photoisomerization Processes of Conjugated Molecules: Role of Hydrogen Migration. J. Chem. Phys. 83, 2348–2362 (1985)
Freund., L., Klessinger, M.: Photochemical Reaction Pathways of Ethylene. Int. J. Quantum Chem. 70, 1023–1028 (1998)
Ben-Nun, M., Martínez, T.J.: Photodynamics of Ethylene: Ab Initio Studies of Conical Intersections. Chem. Phys. 259, 237–248 (2000); Ben-Nun, M., Martínez, T.J.: Ab initio Molecular Dynamics Study of Cis-trans Photoisomerization in Ethylene. Chem. Phys. Lett. 298, 57–65 (1998)
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Lischka, H., Aquino, A.J.A., Barbatti, M., Solimannejad, M. (2005). High-Level Quantum Chemical Methods for the Study of Photochemical Processes. In: Gervasi, O., et al. Computational Science and Its Applications – ICCSA 2005. ICCSA 2005. Lecture Notes in Computer Science, vol 3480. Springer, Berlin, Heidelberg. https://doi.org/10.1007/11424758_104
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DOI: https://doi.org/10.1007/11424758_104
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-25860-5
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