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Frozen natural orbitals for ionized states within equation-of-motion coupled-cluster formalism
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10.1063/1.3276630
/content/aip/journal/jcp/132/1/10.1063/1.3276630
http://aip.metastore.ingenta.com/content/aip/journal/jcp/132/1/10.1063/1.3276630

Figures

Image of FIG. 1.
FIG. 1.

CPU (black circles, values on the left -axis) and the lowest IE of water dimer (red squares, right -axis) as a function of the percentage of virtual NOs retained in the calculation. The calculations were performed using a serial version of Q-CHEM on a 2xXeon EM64T 3.2 GHz machine.

Image of FIG. 2.
FIG. 2.

MEs (upper panel) and STDs (bottom panel) for the six lowest IEs of water dimer at the level using FNOs vs frozen virtual canonical HF orbitals.

Image of FIG. 3.
FIG. 3.

Errors in total energies of the ground and the lowest six ionized states of due to FNO truncation as a function of the total natural occupation retained.

Image of FIG. 4.
FIG. 4.

Energies of the active virtual orbitals for different FNO truncations of the virtual space of beryllium using the 6-311G basis set.

Image of FIG. 5.
FIG. 5.

MEs for the lowest six IEs of water dimer computed by EOM-IP-CCSD using two different cutoff criteria, i.e., POVO (upper panel) and OCCT (lower panel) thresholds.

Image of FIG. 6.
FIG. 6.

The POVO as a function of the total natural occupation retained in water dimer calculations.

Image of FIG. 7.
FIG. 7.

MEs (upper panel) and STD (lower panel) for the lowest six IEs with respect to the total natural occupation retained in the EOM-IP-CC(2,3) calculations of water dimer. The aug-cc-pVTZ values are plotted with an opposite sign for convenience.

Image of FIG. 8.
FIG. 8.

ME for the lowest 12 IEs with respect to the OCCT in the EOM-IP-CCSD/cc-pVTZ calculation of guanine.

Image of FIG. 9.
FIG. 9.

The 12 highest occupied MOs of guanine and the respective Koopmans’ (HF/cc-pVTZ) and correlated (EOM-IP-CC/cc-pVTZ) ionization energies (eV). Orbital type and weights of the leading EOM-IP-CC amplitudes are also shown.

Image of FIG. 10.
FIG. 10.

Energy difference (, hartree) between the FVS and FNO calculations of the state of water dimer using and (EOM-IP-CC/cc-pVTZ). Inset: the PESs of the six lowest states using OCCT (energy is shifted by 150 hartree).

Image of FIG. 11.
FIG. 11.

The PES scan along the dihedral angle of the lowest ionized state of water dimer calculated using FVS (full line and circles, left -axis) and FNO with (dashed line and empty circles, right -axis). The energies are shifted by 152 hartree.

Tables

Generic image for table
Table I.

12 lowest IEs (eV) of guanine: Koopmans’ energies (the respective MO number is given in parenthesis) and the EOM-IP-CCSD IEs computed in the FVS and by XFNO (the weight of the leading MO is shown in parenthesis). The results of the ultraviolet photoelectron spectroscopy measurements and the synchrotron radiation valence-shell photoionization spectra are also shown (band assignment is given in parentheses).

Generic image for table
Table II.

Average NPEs (kcal/mol) of the water dimer cation for different FNO scans (the number of active NOs is given in parenthesis), EOM-IP-CC/cc-pVTZ.

Generic image for table
Table III.

The effect of diffuse functions and triple excitations on the DEs (mhartree) of the water dimer cation using FVS (unrelaxed estimates, see text). At the bottom part, the values for EOM-IP-CC/cc-pVTZ plus additive corrections from diffuse functions and triple excitations are shown.

Generic image for table
Table IV.

Average NPEs and MEs for the DEs (ME) for , kcal/mol.

Generic image for table
Table V.

The EOM-IP-CCSD/aug-cc-pVTZ NPEs (kcal/mol) along the interfragment separation scan for different OCCT thresholds with and without account of orbital degeneracy, as well as the POVO results. The number of active FNOs along the scan is shown in parenthesis.

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/content/aip/journal/jcp/132/1/10.1063/1.3276630
2010-01-06
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Frozen natural orbitals for ionized states within equation-of-motion coupled-cluster formalism
http://aip.metastore.ingenta.com/content/aip/journal/jcp/132/1/10.1063/1.3276630
10.1063/1.3276630
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