Electronic states of bis(phthalocyaninato)lutetium radical and its related compounds: the application of localized orbital basis set to open-shell phthalocyanine dimers

The energy levels of the lower valence and Rydberg states of selenoformaldehyde, CH2Se, have been calculated by the SCF/CI method. Wavefunctions for the ROHF (restricted open shell Hartree–Fock) states were obtained with the Binnings–Curtis double-ζ basis set, augmented with Rydberg and polarization functions. Configuration interaction was applied to the parent configurations, PCMO (parent configuration molecular orbital). Oscillator strengths were evaluated for the allowed electric dipole transitions by the RPA (random phase approximation), and SOPPA (second-order polarization propagator approximation) methods. The spin-orbit contribution to the zero field splitting of the first triplet state, 3A2(n,π*) as well as the oscillator strengths to the three spin components were calculated by perturbation theory. These calculations predict that the Sx, Sy, and Sz components are shifted by −96.091,−96.707, and + 29.167 cm−1, respectively, from their unperturbed position. The oscillator strengths for the three components fx, fy, and fz of the 3A2(n,π*) ← 1A1(g.s.) transition were calculated to be 3.45 × 10−7, 1.15 × 10−7, and 173.0 × 10−7.

Download Full-text

Erratum: A Self-Consistent Crank-Nicolson Method for Solving Time-Dependent Kohn-Sham Equation in a Localized Atomic Orbital Basis Set

New Physics Sae Mulli ◽

10.3938/npsm.70.908 ◽

2020 ◽

Vol 70 (10) ◽

pp. 908-908

Author(s):

Junhyeok BANG*

Keyword(s):

Atomic Orbital ◽

Time Dependent ◽

Basis Set ◽

Orbital Basis ◽

Sham Equation ◽

Self Consistent ◽

Crank Nicolson

Download Full-text

The structure and energetics of low-lying states of RCO and RNN free radicals

Canadian Journal of Chemistry ◽

10.1139/v77-120 ◽

1977 ◽

Vol 55 (5) ◽

pp. 863-868 ◽

Cited By ~ 20

Author(s):

N. Colin Baird ◽

Harish B. Kathpal

Keyword(s):

Experimental Data ◽

Free Radicals ◽

Hydrogen Atom ◽

Ab Initio ◽

Open Shell ◽

Basis Set ◽

Basis Sets ◽

Mo Calculations ◽

Decomposition Products ◽

Ab Initio Mo Calculations

The important geometrical variables in the structures of the lowest 2A′ and 2A′′ states of the free radicals HCO, CH3CO, NH2CO, HNN, and CH3NN have been determined by ab initio MO calculations using the STO-3G basis set. The energy differences between the states, and the energies of the radicals relative to their decomposition products and relative to their hydrogen atom addition products, are reported using both STO-3G and 4-31G basis sets in the restricted open-shell calculations. The trends in these results and their relation to available experimental data are discussed.

Download Full-text

Accuracy Assessment of the ROHF-CCSD(T) Calculationsof Dipole Moments of Small Radicals

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19981409 ◽

1998 ◽

Vol 63 (9) ◽

pp. 1409-1430 ◽

Cited By ~ 18

Author(s):

Miroslav Urban ◽

Pavel Neogrády ◽

Juraj Raab ◽

Geerd H. F. Diercksen

Keyword(s):

Large Deviation ◽

Theoretical Calculations ◽

Dipole Moments ◽

Accuracy Assessment ◽

Open Shell ◽

Basis Set ◽

Coupled Cluster ◽

Hartree Fock ◽

Experimental Values

Dipole moments of a series of radicals, OH, NO, NS, SF, SO, PO, ClO, CN, LiO, NO2, and ClO2 were calculated by the Coupled Cluster CCSD(T) method with the single determinant restricted open shell Hartree-Fock (ROHF) reference. For all molecules theoretical dipole moments were carefully compared to experimental values. The size and the quality of the basis set were systematically improved. Spin adaptation in the ROHF-CCSD(T) method, largest single and double excitation amplitudes and the T1 diagnostics were considered as indicators in the quality assessment of calculated dipole moments. For most molecules the accuracy within 0.01-0.03 D was readily obtained. For ClO and CN the spin adaptation was necessary - its contribution was as large as 0.03-0.045 D. Large deviation from experiment is observed for OH in its A2Σ+ excited state (0.135 D) and especially for LiO in its 2Π ground state (0.22 D). No indication of the failure of theoretical calculations was found which leads to the conclusion that, even if there is still a space for the improvement of theoretical calculations, experimental values should be reconsidered.

Download Full-text