Optimizing Conical Intersections without Derivative Coupling Vectors:  Application to Multistate Multireference Second-Order Perturbation Theory (MS-CASPT2)

Levine, Bernard B.; Coe, Joshua D.; Martı́nez, Todd J.

doi:10.1021/jp0761618

Cited by 378 publications

(523 citation statements)

References 56 publications

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“…50 It has been confirmed that at all MECIs reported in this work the energy differences between the two relevant electronic states are less than ~0.1 eV at the MS-CASPT2 level used to determine the MECI geometries.…”

Section: Computational Detailssupporting

confidence: 71%

“…The MECI search is also performed at the MS-CASPT2 level since the MECI points determined by SA-CASSCF or SS-CASPT2 are often quite different from those obtained by MS-CASPT2. The MECI search between the i-and j-th electronic states (i = j+1) is performed by a penalty-function approach proposed by Levine et al,50 where the following function is minimized…”

Section: Computational Detailsmentioning

confidence: 99%

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Photophysics of cytosine tautomers: new insights into the nonradiative decay mechanisms from MS-CASPT2 potential energy calculations and excited-state molecular dynamics simulations

Nakayama

Harabuchi

Yamazaki

et al. 2013

Phys. Chem. Chem. Phys.

111

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A comprehensive picture of the ultrafast nonradiative decay mechanisms of three cytosine tautomers (amino-keto, imino-keto, and amino-enol forms) is revealed by high-level ab initio potential energy calculations using the multistate (MS) CASPT2 method and also by on-the-fly excited-state molecular dynamics simulations employing the CASSCF method. To obtain a reliable potential energy profile along the deactivation pathways, the MS-CASPT2 method is employed even for the optimization of minimum energy structures in the excited state and conical intersection (CI) structures between the ground and excited states. In the imino (imino-keto) form, we locate a new CI structure involving the twisting of the imino group, and the decay pathway leading to this CI is found to be barrierless, suggesting a remarkably efficient deactivation of imino cytosine. In the keto (amino-keto) form, the MS-CASPT2 calculations exhibit an efficient decay path to the ethylene-like CI involving the twisting of C-C double bond in the six-membered ring, with a barrier of ~0.08 eV from the minimum of the 1 ππ* state. In the enol (amino-enol) form, three types of CIs are identified for the first time. Among them, the ethylene-like CI with a similar molecular structure to the keto form provides the most preferred deactivation pathway of enol cytosine. This pathway exhibits a higher barrier of ~0.22 eV and a higher energy of CI than those of keto cytosine. Nonadiabatic molecular dynamics simulations provide a time-dependent picture of the deactivation processes, including the excited-state lifetime of each tautomer. In particular, the decay time of the imino tautomer is predicted to be only ~100 fs. Our computational results are in remarkably good agreement with the experimental findings in recent femtosecond pump-probe photoionization spectroscopy [J. Am. Chem. Soc. 131, 16939 (2009); J. Phys. Chem. A 115, 8406 (2011)], supporting the coexistence of more than one tautomer in the photophysics of isolated cytosine and that each tautomer exhibits a different excited-state lifetime.1

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Section: Computational Detailssupporting

confidence: 71%

Section: Computational Detailsmentioning

confidence: 99%

Photophysics of cytosine tautomers: new insights into the nonradiative decay mechanisms from MS-CASPT2 potential energy calculations and excited-state molecular dynamics simulations

Nakayama

Harabuchi

Yamazaki

et al. 2013

Phys. Chem. Chem. Phys.

111

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“…27 Although the MSPT2 method was used some time ago for minimal energy conical intersection optimization, 28 it has only recently been used in nonadiabatic dynamics simulations. 15 However, the lack of analytical nonadiabatic coupling vectors at the MSPT2 level has been an obstacle to widespread use for both intersection optimization and nonadiabatic dynamics.…”

Section: Introductionmentioning

confidence: 99%

Role of Rydberg States in the Photochemical Dynamics of Ethylene

et al. 2012

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/jp2097185Access and use of this website and the material on it are subject to the Terms and Conditions set forth atThe role of Rydberg states in the photochemical dynamics of ethylene Mori, Toshifumi; Glover, William J.; Schuurman, Michael S.; Martinez, Todd J.http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/droits L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site

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“…Maeda et al 65 have shown that the branching-plane (BP) updating method is an efficient algorithm to locate CI points, because the method does not require the nonadiabatic coupling matrix elements (NACMEs) that are missing or computationally demanding for some correlated electronic structure methods. Although the penalty-constrained optimization 39,66 was adopted in the previous studies, 56,57 a comparative study at the semiempirical configuration-interaction level has shown that the penalty-constrained method needs many more optimization steps. 67 The organization of this paper is as follows.…”

Section: -2mentioning

confidence: 99%

“…39,66 As described in Sec. II B, the BP updating method was adopted in this work since the NACME for SFDFT is not available in the current version of GAMESS.…”

Section: Computational Detailsmentioning

confidence: 99%

Optimizing conical intersections of solvated molecules: The combined spin-flip density functional theory/effective fragment potential method

Minezawa

Gordon

2012

The Journal of Chemical Physics

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Solvent effects on a potential energy surface crossing are investigated by optimizing a conical intersection (CI) in solution. To this end, the analytic energy gradient has been derived and implemented for the collinear spinflip density functional theory (SFDFT) combined with the effective fragment potential (EFP) solvent model. The new method is applied to the azomethane-water cluster and the chromophore of green fluorescent protein in aqueous solution. These applications illustrate not only dramatic changes in the CI geometries but also strong stabilization of the CI in a polar solvent. Furthermore, the CI geometries obtained by the hybrid SFDFT/EFP scheme reproduce those by the full SFDFT, indicating that the SFDFT/EFP method is an efficient and promising approach for understanding nonadiabatic processes in solution. Solvent effects on a potential energy surface crossing are investigated by optimizing a conical intersection (CI) in solution. To this end, the analytic energy gradient has been derived and implemented for the collinear spin-flip density functional theory (SFDFT) combined with the effective fragment potential (EFP) solvent model. The new method is applied to the azomethane-water cluster and the chromophore of green fluorescent protein in aqueous solution. These applications illustrate not only dramatic changes in the CI geometries but also strong stabilization of the CI in a polar solvent. Furthermore, the CI geometries obtained by the hybrid SFDFT/EFP scheme reproduce those by the full SFDFT, indicating that the SFDFT/EFP method is an efficient and promising approach for understanding nonadiabatic processes in solution.

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Optimizing Conical Intersections without Derivative Coupling Vectors: Application to Multistate Multireference Second-Order Perturbation Theory (MS-CASPT2)

Cited by 378 publications

References 56 publications

Photophysics of cytosine tautomers: new insights into the nonradiative decay mechanisms from MS-CASPT2 potential energy calculations and excited-state molecular dynamics simulations

Photophysics of cytosine tautomers: new insights into the nonradiative decay mechanisms from MS-CASPT2 potential energy calculations and excited-state molecular dynamics simulations

Role of Rydberg States in the Photochemical Dynamics of Ethylene

Optimizing conical intersections of solvated molecules: The combined spin-flip density functional theory/effective fragment potential method

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