Electronic excitation energies in solution at equation of motion CCSD level within a state specific polarizable continuum model approach

Caricato, Marco; Mennucci, Benedetta; Scalmani, Giovanni; Trucks, Gary W.; Frisch, Michael J.

doi:doi:10.1063/1.3314221

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Efficient computation of free energy of crystal phases due to external potentials by error-biased Bennett acceptance ratio method

Free energy of crystal phases is commonly evaluated by thermodynamic integration along a reversible path that involves an external potential. However, this method suffers from the hysteresis caused by the differences in the center of mass position of the crystal phase in the presence and absence of the external potential. To alleviate this hysteresis, a constraint on the translational degrees of freedom of the crystal phase is imposed along the path and subsequently a correction term is added t...

Quantum dynamics of the H+CH₄→H₂+CH₃ reaction in curvilinear coordinates: Full-dimensional and reduced dimensional calculations of reaction rates

Full-dimensional quantum dynamics calculations for the H+CH4→H2+CH3 reaction using curvilinear coordinates are presented. A curvilinear coordinate system to describe reactions of the type X+YCH3→XY+CH3 is developed which facilitates efficient calculations using the multiconfigurational time-dependent Hartree (MCTDH) approach. To describe the bending motion of the X and Y atoms relative to the axis defined by the CH3 fragment, coordinates based on stereographic projection are introduced. These c...

We present a study of excitation energies in solution at the equation of motion coupled cluster singles and doubles (EOM-CCSD) level of theory. The solvent effect is introduced with a state specific polarizable continuum model (PCM), where the solute-solvent interaction is specific for the state of interest. Three definitions of the excited state one-particle density matrix (1PDM) are tested in order to gain information for the development of an integrated EOM-CCSD/PCM method. The calculations show the accuracy of this approach for the computation of such property in solution. Solvent shifts between nonpolar and polar solvents are in good agreement with experiment for the test cases. The completely unrelaxed 1PDM is shown to be a balanced choice between computational effort and accuracy for vertical excitation energies, whereas the response of the ground state CCSD amplitudes and of the molecular orbitals is important for other properties, as for instance the dipole moment.

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INTRODUCTION
COMPUTATIONAL DETAILS
RESULTS
CONCLUSIONS

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KEYWORDS and PACS

Keywords

coupled cluster calculations, electric moments, excited states, ground states, molecular electronic states, molecular moments, solvent effects, spectral line shift

PACS

31.70.Dk

Environmental and solvent effects
31.15.bw

Coupled-cluster theory
33.70.Jg

Line and band widths, shapes, and shifts
33.15.Kr

Electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility

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http://dx.doi.org/10.1063/1.3314221

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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