Calculation of the fine structure of the triplet state $$\tilde a^3 A_2 $$ of the ozone molecule by the method of multiconfiguration self-consistent field

Minaev, B. F.; Khomenko, E. M.; Bilan, E. A.; Yashchuk, L. B.

doi:10.1134/1.1870062

Cited by 11 publications

(14 citation statements)

References 8 publications

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“…Linewidths are computed for a non rotating molecule, which makes our treatment analogous to the zero-field splitting problem. 13,14 Small spin-spin coupling 8,14 is neglected. Figure 1 depicts cuts along the bond angle ␣ through the PESs of four adiabatic electronic states at energies close to the dissociation threshold.…”

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confidence: 99%

Spin-orbit mechanism of predissociation in the Wulf band of ozone

Grebenshchikov

Zhu

et al. 2006

The Journal of Chemical Physics

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Previously calculated resonance widths of the ground vibrational levels in the electronic states 1 (3)A" ((3)A(2)) and 1 (3)A' ((3)B(2)), which belong to the Wulf band system of ozone, are significantly smaller than observed experimentally. We demonstrate that predissociation is drastically enhanced by spin-orbit coupling between 1 (3)A"/X (1)A' and 1 (3)A'/1 (3)A". Multistate quantum mechanical calculations using ab initio spin-orbit coupling matrix elements give linewidths of optically bright components of the right order of magnitude.

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Spin-orbit mechanism of predissociation in the Wulf band of ozone

Grebenshchikov

Zhu

et al. 2006

The Journal of Chemical Physics

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“…Several approaches such as coupled-perturbed SCF, 38,39 spin density functional theory and perturbation theory (SDFT-PT), 40,41 Douglas-Kroll-Hess ansatz, 42 spin-orbit configuration interaction (CI), 43,44 and sum-over-states (SOS) approaches [33][34][35][36][37][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] have been proposed for D SO tensor calculations. In the spin-orbit CI and SOS approaches, excited states are explicitly solved, and thus sophisticated and balanced descriptions of both the ground and excited states are required.…”

Section: Introductionmentioning

confidence: 99%

“…For the D SS tensor calculations, many theoretical works based on semi-empirical, 29,30,[66][67][68][69][70][71] ab initio, 33,[35][36][37][54][55][56][57][58][59][60][61][72][73][74][75][76][77][78] and DFT 34,[51][52][53][78][79][80][81][82][83][84][85] methods have been documented. MCSCF-based approaches such as CASSCF and multireference (MR)-CI can provide quantitatively correct D SS tensors.…”

Section: Introductionmentioning

confidence: 99%

“…MCSCF-based approaches such as CASSCF and multireference (MR)-CI can provide quantitatively correct D SS tensors. 33,35,36,[54][55][56][57][58][59][60][61][75][76][77] Indeed, these methods are reliable but computationally rather demanding. The first DFT application to D SS tensors was reported in 2002 by Petrenko et al, 80 who used the McWeeny and Mizuno equation 86 with the spin density matrices constructed from the restricted open-shell (RO) Kohn-Sham determinant.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio and DFT studies of the spin–orbit and spin–spin contributions to the zero-field splitting tensors of triplet nitrenes with aryl scaffolds

Sugisaki

Toyota

Sato

et al. 2011

Phys. Chem. Chem. Phys.

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Spin-orbit and spin-spin contributions to the zero-field splitting (ZFS) tensors (D tensors) of spin-triplet phenyl-, naphthyl-, and anthryl-nitrenes in their ground state are investigated by quantum chemical calculations, focusing on the effects of the ring size and substituted position of nitrene on the D tensor. A hybrid CASSCF/MRMP2 approach to the spin-orbit term of the D tensor (D(SO) tensor), which was recently proposed by us, has shown that the spin-orbit contribution to the entire D value, termed the ZFS parameter or fine-structure constant, is about 10% in all the arylnitrenes under study and less depends on the size and connectivity of the aryl groups. Order of the absolute values for D(SO) can be explained by the perturbation on the energy level and spatial distributions of π-SOMO through the orbital interaction between SOMO of the nitrene moiety and frontier orbitals of the aryl scaffolds. Spin-spin contribution to the D tensor (D(SS) tensor) has been calculated in terms of the McWeeny-Mizuno equation with the DFT/EPR-II spin densities. The D(SS) value calculated with the RO-B3LYP spin density agrees well with the D(Exptl) -D(SO) reference value in phenylnitrene, but agreement with the reference value gradually becomes worse as the D value decreases. Exchange-correlation functional dependence on the D(SS) tensor has been explored with standard 23 exchange-correlation functionals in both RO- and U-DFT methodologies, and the RO-HCTH/407 method gives the best agreement with the D(Exptl) -D(SO) reference value. Significant exchange-correlation functional dependence is observed in spin-delocalized systems such as 9-anthrylnitrene (6). By employing the hybrid CASSCF/MRMP2 approach and the McWeeny-Mizuno equation combined with the RO-HCTH/407/EPR-II//U-HCTH/407/6-31G* spin densities for D(SO) and D(SS), respectively, a quantitative agreement with the experiment is achieved with errors less than 10% in all the arylnitrenes under study. Guidelines to the putative approaches to D(SS) tensor calculations are given.

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“…The study of the mechanisms underlying the photocatalytic cycle of the decomposition of O 3 in the atmosphere has initiated detailed investigations of the effects of spin-orbital interaction in the absorption spectra and reactions of the photolysis of ozone [3][4][5][6]. In [4][5][6][7], particular emphasis was given to the role of excited triplet states in the absorption spectrum of ozone as well as to the analysis of the nature of the fine structure of states with allowance for the contributions of spin-orbital and spin-spin interactions.In the present work, we carried out calculation of the electrical and magnetic properties of an ozone molecule in the ground singlet state that greatly depend on the electronic excitations of the molecule. It should be noted that the electronic structure of the ground X 1 A 1 state of the O 3 molecule is similar to the biradical that has two unpaired electrons on end atoms of oxygen weakly bound into a singlet state.…”

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Calculation of properties of the ozone molecule by the multiconfigurational self-consistent field method

Minaev

Khomenko

2005

J Appl Spectrosc

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For the ground state of the ozone molecule, by using the multiconfigurational self-consistent field method, we calculated the electric and magnetic properties -quadrupole moment, polarizability, tensor of magnetic susceptibility, nuclear quadrupole interaction constant, and the rotational g-factor. Qualitative agreement between the calculated parameters and experimental values was obtained. The tensors of chemical shielding in the spectrum of the nuclear magnetic resonance for the 17 O isotopes have also been predicted (without allowance for the contribution made by the spin of the electrons).Introduction. In recent years, much attention has been paid to the electron structure and photochemistry of the ozone molecule [1,2]. The study of the mechanisms underlying the photocatalytic cycle of the decomposition of O 3 in the atmosphere has initiated detailed investigations of the effects of spin-orbital interaction in the absorption spectra and reactions of the photolysis of ozone [3][4][5][6]. In [4][5][6][7], particular emphasis was given to the role of excited triplet states in the absorption spectrum of ozone as well as to the analysis of the nature of the fine structure of states with allowance for the contributions of spin-orbital and spin-spin interactions.In the present work, we carried out calculation of the electrical and magnetic properties of an ozone molecule in the ground singlet state that greatly depend on the electronic excitations of the molecule. It should be noted that the electronic structure of the ground X 1 A 1 state of the O 3 molecule is similar to the biradical that has two unpaired electrons on end atoms of oxygen weakly bound into a singlet state. The biradical structure of the ground state of ozone leads to a situation where the properties of this molecule cannot be explained on the basis of calculation of the wave function by the Hartree-Fock method for closed shells. An important criterion of the accuracy of the wave function is provided by calculation of the observed properties of the molecule such as polarizability, dipole and quadrupole moments, as well as the parameters of the fine structure determined experimentally by the methods of radiospectroscopy. An analysis of rotational spectra, nuclear quadrupole resonance, and the Zeeman effect allows one to relate the observed properties to the characteristic features of the electronic structure of this unusual molecule. An especially important role should be played by the magnetic properties of the electron shell -the magnetic susceptibility tensor and the parameters of the nuclear magnetic resonance (NMR) spectrum for the isotopes of 17 O. Although the 17 O NMR spectra are very complex for experimental investigation for a whole number of reasons (the high rate of spin relaxation, the availability of the quadrupole moment of the nucleus, the low natural content of the isotope), recently works dealing with investigation of the NMR spectra of ozone have appeared.In the present work, these properties are calculated by the method of quadra...

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Calculation of the fine structure of the triplet state $$\tilde a^3 A_2 $$ of the ozone molecule by the method of multiconfiguration self-consistent field

Cited by 11 publications

References 8 publications

Spin-orbit mechanism of predissociation in the Wulf band of ozone

Spin-orbit mechanism of predissociation in the Wulf band of ozone

Ab initio and DFT studies of the spin–orbit and spin–spin contributions to the zero-field splitting tensors of triplet nitrenes with aryl scaffolds

Calculation of properties of the ozone molecule by the multiconfigurational self-consistent field method

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