Abstract
Static hyperpolarizabilities of molecules (water, acetonitrile, chloroform, and para-nitroaniline) are calculated with large basis sets using coupled-cluster response theory and compared to four common density functional theory methods. These results reveal which methods and basis sets are appropriate for nonlinear optical studies for different types of molecules and provide a means for estimating errors from the quantum chemical approximation when including vibrational contributions or solvent effects at the QM/MM level. The largest calculation reported, which was for 72 electrons in 812 functions at symmetry, took only a few hours on 256 nodes demonstrating that even larger calculations are quite feasible using modern supercomputers.
J.R.H. was supported by the DOE-CSGF program provided under Grant No. DE-FG02-97ER25308 and thanks Dr. Peng-Dong Fan for generous hospitality for the 2 week period when the CCSD-QR code was written.
This research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.
This research used resources of the Argonne Leadership Computing Facility at Argonne National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357.
I. INTRODUCTION
II. THEORY AND COMPUTATIONAL DETAILS
III. RESULTS
A. Water
B. Acetonitrile
C. Chloroform
D. para-nitroaniline
IV. CONCLUSIONS
Key Topics
- Basis sets
- 55.0
- Density functional theory
- 20.0
- Electrical properties
- 18.0
- Polarizability
- 12.0
- Electric dipole moments
- 11.0
Figures
Basis set convergence of the three unique tensor components composite and parallel static hyperpolarizability of .
Basis set convergence of the three unique tensor components composite and parallel static hyperpolarizability of .
Basis set convergence of the three unique tensor components composite and parallel static hyperpolarizability of .
Basis set convergence of the three unique tensor components composite and parallel static hyperpolarizability of .
Basis set convergence of the three unique tensor components composite and parallel static hyperpolarizability of .
Basis set convergence of the three unique tensor components composite and parallel static hyperpolarizability of .
Tables
Hyperpolarizabilities of within the hierarchy of coupled-cluster methods. See the references given for geometry information and other calculation details. All quantities are given in atomic units.
Hyperpolarizabilities of within the hierarchy of coupled-cluster methods. See the references given for geometry information and other calculation details. All quantities are given in atomic units.
Electric properties of at the CCSD level using various basis sets (spherical, frozen core). All quantities are given in atomic units.
Electric properties of at the CCSD level using various basis sets (spherical, frozen core). All quantities are given in atomic units.
Comparison of basis sets for electric properties of at the CCSD level. Pure angular functions where used, as was the frozen core approximation. All quantities are given in atomic units. The -axis is unique while the - and -axes are degenerate. The CCSD iterations did not converge with the t-aug-cc-pVQZ basis set.
Comparison of basis sets for electric properties of at the CCSD level. Pure angular functions where used, as was the frozen core approximation. All quantities are given in atomic units. The -axis is unique while the - and -axes are degenerate. The CCSD iterations did not converge with the t-aug-cc-pVQZ basis set.
Comparison of CCSD and DFT electric properties of with the d-aug-cc-pVTZ basis set. All quantities are given in atomic units. The -axis is unique while the - and -axes are degenerate. Due to the different orientations used in NWCHEM and DALTON, the sign of the dipole moment and one component of the hyperpolarizability tensor for CCSD and the other methods have opposite sign, but this has no effect on .
Comparison of CCSD and DFT electric properties of with the d-aug-cc-pVTZ basis set. All quantities are given in atomic units. The -axis is unique while the - and -axes are degenerate. Due to the different orientations used in NWCHEM and DALTON, the sign of the dipole moment and one component of the hyperpolarizability tensor for CCSD and the other methods have opposite sign, but this has no effect on .
Comparison basis sets for electric properties of at the CCSD level. Pure angular functions where used, as was the frozen core approximation. All quantities are given in atomic units. The -axis is unique while the - and -axes are degenerate. The CCSD iterations did not converge with the t-aug-cc-pVQZ basis set.
Comparison basis sets for electric properties of at the CCSD level. Pure angular functions where used, as was the frozen core approximation. All quantities are given in atomic units. The -axis is unique while the - and -axes are degenerate. The CCSD iterations did not converge with the t-aug-cc-pVQZ basis set.
Comparison of CCSD and DFT electric properties of with the d-aug-cc-pVTZ basis set. All quantities are given in atomic units. The -axis is unique while the - and -axes are degenerate. Due to the different orientations used in NWCHEM and DALTON, the sign of the dipole moment and one component of the hyperpolarizability tensor for CCSD and the other methods have opposite sign, but this has no effect on .
Comparison of CCSD and DFT electric properties of with the d-aug-cc-pVTZ basis set. All quantities are given in atomic units. The -axis is unique while the - and -axes are degenerate. Due to the different orientations used in NWCHEM and DALTON, the sign of the dipole moment and one component of the hyperpolarizability tensor for CCSD and the other methods have opposite sign, but this has no effect on .
Electric properties of para-nitroaniline at the CCSD level using various basis sets (spherical, frozen core). All quantities are given in atomic units.
Electric properties of para-nitroaniline at the CCSD level using various basis sets (spherical, frozen core). All quantities are given in atomic units.
Comparison of CCSD to other methods for the electric properties of para-nitroaniline with the aug-cc-pVTZ basis set. All quantities are given in atomic units. Due to the different orientations used in NWCHEM and DALTON, the sign of the dipole moment for CCSD and the other methods have opposite sign; the other properties are not affected. The CCS and CC2 methods were computational intractable with the aug-cc-pVTZ basis.
Comparison of CCSD to other methods for the electric properties of para-nitroaniline with the aug-cc-pVTZ basis set. All quantities are given in atomic units. Due to the different orientations used in NWCHEM and DALTON, the sign of the dipole moment for CCSD and the other methods have opposite sign; the other properties are not affected. The CCS and CC2 methods were computational intractable with the aug-cc-pVTZ basis.
Geometry effects on PNA at the CCSD/aug-cc-pVDZ level. Geometries from this work were optimized at the B3LYP/cc-pVTZ level whereas that of Ref. 40 is based upon crystallographic data (see paper for details).
Geometry effects on PNA at the CCSD/aug-cc-pVDZ level. Geometries from this work were optimized at the B3LYP/cc-pVTZ level whereas that of Ref. 40 is based upon crystallographic data (see paper for details).
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