Dynamic polarizabilities of polyaromatic hydrocarbons using coupled-cluster linear response theory

Hammond, Jeff R.; Kowalski, Karol; deJong, Wibe A.

doi:doi:10.1063/1.2772853

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Basis set limits of the second order Møller-Plesset correlation energies of water, methane, acetylene, ethylene, and benzene

We report second order Møller-Plesset (MP2) and MP2-F12 total energies on He, Ne, Ar, H2O, CH4, C2H2, C2H4, and C6H6, using the correlation consistent basis sets, aug-cc-pVXZ (X = D−7). Basis set extrapolation techniques are applied to the MP2 and MP2-F12/B methods. The performance of the methods is tested in the calculations of the atoms, He, Ne, and Ar. It is indicated that the two-point extrapolation of MP2-F12/B with the basis sets (X = 5,6) is the most reliable. Similar accuracy is obtaine...

Efficient evaluation of analytic vibrational frequencies in Hartree-Fock and density functional theory for periodic nonconducting systems

We report a method for the efficient evaluation of analytic energy second derivatives with respect to in-phase nuclear coordinate displacements within Hartree-Fock and Kohn-Sham density functional theories using Gaussian orbitals and periodic boundary conditions. The use of an atomic orbital formulation for all computationally challenging steps allows us to adapt the direct space fast multipole method for the Coulomb-type infinite summations. Our implementation also exploits the local character...

Coupled-cluster theory with single and double excitations is applied to the calculation of optical properties of large polyaromatic hydrocarbons. Dipole polarizabilities are reported for benzene, pyrene, and the oligoacenes sequence n = 2–6. Dynamic polarizabilities were calculated on polyacences as large as pentacene for a single frequency and for benzene and pyrene at many frequencies. The basis set effect was studied for benzene using a variety of basis sets in the Pople [Theor. Chim. Acta 28, 213 (1973)] and Dunning [J. Chem. Phys. 90, 1007 (1989)] families up to aug-cc-pVQZ and the Sadlej pVTZ basis [ Collect. Czech. Chem. Commun. 53, 1995 (1998)] , which was used exclusively for the largest molecules. Geometries were optimized using HF, B3LYP, PBE0, and MP2 and compared to experiment to measure method dependence and the possible role of bond-length alternation. Finally, the polarizability results were compared to four common density functionals (B3LYP, BLYP, PBE0, PBE).

Article Outline

INTRODUCTION
THEORY AND COMPUTATIONAL DETAILS
RESULTS
1. Basis set convergence
2. Importance of iterative triples
3. Geometry effects
4. Comparison of density-functional and coupled-cluster polarizabilities for linear oligoacenes
5. Accuracy of frequency-dependent polarizabilities
CONCLUSIONS

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KEYWORDS and PACS

Keywords

bond lengths, coupled cluster calculations, density functional theory, HF calculations, molecular configurations, organic compounds, polarisability

PACS

31.15.bw

Coupled-cluster theory
31.15.xr

Self-consistent-field methods
31.15.E-

Density-functional theory
33.15.Kr

Electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility
33.15.Dj

Interatomic distances and angles
33.15.Bh

General molecular conformation and symmetry; stereochemistry

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http://link.aip.org/link/doi/10.1063/1.2772853

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0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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