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Vertical transition energies (in eV) at the equilibrium distance re = 2.667 A of the X 'X+ ground state. they estimated the missing correlation contribution by taking the difference be- tween the computed ground state potential curve and the experimental RKR one, and adding this estimate to the energy of the excited states. The computed potential energy curves are shown in Figure 2, and the vertical transition ener- gies corresponding to the experimentally known valence states are displayed in Table 3, along with the theoretical results discussed here.

Figure 2 Vertical transition energies (in eV) at the equilibrium distance re = 2.667 A of the X 'X+ ground state. they estimated the missing correlation contribution by taking the difference be- tween the computed ground state potential curve and the experimental RKR one, and adding this estimate to the energy of the excited states. The computed potential energy curves are shown in Figure 2, and the vertical transition ener- gies corresponding to the experimentally known valence states are displayed in Table 3, along with the theoretical results discussed here.

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Figure 1. Iodine atomic data in atomic units from reference [37]. The scalar- relativistic all-electron 5p orbital in dotted line, the corresponding 5p pseudoor- bital in dashed line, and the 5p-spin-orbit pseudopotential in plain line.
Figure 1. Iodine atomic data in atomic units from reference [37]. The scalar- relativistic all-electron 5p orbital in dotted line, the corresponding 5p pseudoor- bital in dashed line, and the 5p-spin-orbit pseudopotential in plain line.
Equilibrium distances r, and dissociation energies D, for the ground state of molecular iodine, from Ref. [97].
Equilibrium distances r, and dissociation energies D, for the ground state of molecular iodine, from Ref. [97].
Spectroscopic data for AgCl and AgI. MRCI, CC, CC+SO and experimental data are taken from Ref. [117] and references therein, MRCI2 from Refs. [118, 121] and all- electron ZORA calculations from Ref. [133]. | The value in parentheses refers to the second minimum at longer distances.
Spectroscopic data for AgCl and AgI. MRCI, CC, CC+SO and experimental data are taken from Ref. [117] and references therein, MRCI2 from Refs. [118, 121] and all- electron ZORA calculations from Ref. [133]. | The value in parentheses refers to the second minimum at longer distances.
The agreement between the calculated energies reported in Table 6 and ex- perimental data is satisfactory, even though one should keep in mind that the calculations do not treat the specific interactions between the ionic lattice and the neptuny] ion, a point that will be developed in more detail in the next sec- tion 3.2. In particular, the two highest calculated states are badly reproduced, possibly because interactions with higher states or with the ions of the lattice are missing. By analysing the nature of each fine-structure components in terms of A-S states, the authors assigned the first three excited states to pure atomic combinations of the f orbitals. The fourth state involves excitations from the bonding orbital oy to the essentially atomic f non bonding orbitals (dy, @y) and has a charge-transfer character. The presence of low-lying charge-transfer excitations is an important difference from the spectrum of the urany] ion [155]. In the same way and using the same theoretical method, the authors studied the more complicated monocationic NpO; which has two unpaired f electrons in the around state. This ion is isoelectronic to PuO2+. which will be discussed calculated the vertical transitions at the ground state geometry (re = 1.66 A) and correlated all valence orbitals with the exception of the low-lying ones, namely the log and 20g, the 1oy and the 17g, resulting in a double group CI space of 4 million double group configurations.
The agreement between the calculated energies reported in Table 6 and ex- perimental data is satisfactory, even though one should keep in mind that the calculations do not treat the specific interactions between the ionic lattice and the neptuny] ion, a point that will be developed in more detail in the next sec- tion 3.2. In particular, the two highest calculated states are badly reproduced, possibly because interactions with higher states or with the ions of the lattice are missing. By analysing the nature of each fine-structure components in terms of A-S states, the authors assigned the first three excited states to pure atomic combinations of the f orbitals. The fourth state involves excitations from the bonding orbital oy to the essentially atomic f non bonding orbitals (dy, @y) and has a charge-transfer character. The presence of low-lying charge-transfer excitations is an important difference from the spectrum of the urany] ion [155]. In the same way and using the same theoretical method, the authors studied the more complicated monocationic NpO; which has two unpaired f electrons in the around state. This ion is isoelectronic to PuO2+. which will be discussed calculated the vertical transitions at the ground state geometry (re = 1.66 A) and correlated all valence orbitals with the exception of the low-lying ones, namely the log and 20g, the 1oy and the 17g, resulting in a double group CI space of 4 million double group configurations.
' The 0- of the 2M, state was omitted in Ref. [157]. Vertical transition energies in kcal.mol~! of the Pud3t molecule cal- culated at the SDCI+Q level without and with spin- orbit coupling at Te = 1.6770 A, taken from Ref. [157].
' The 0- of the 2M, state was omitted in Ref. [157]. Vertical transition energies in kcal.mol~! of the Pud3t molecule cal- culated at the SDCI+Q level without and with spin- orbit coupling at Te = 1.6770 A, taken from Ref. [157].
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