The <i>A</i>→<i>X</i> system of Ni2 in argon matrices

Ahmed, Fakhruddin; Nixon, Eugene R.

doi:10.1063/1.438750

Cited by 37 publications

(5 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The data describing these curves are in Table 2 . GVVPT2 predicted the ππ–hole states to lie higher in energy than the δπ–hole states, in agreement with previous studies ( Ahmed and Nixon, 1979 ; Rasanen et al, 1987 ; Russo et al, 1994 ). For all four δπ–hole states studied, the major CSFs involved a doubly occupied 4sσ g bonding orbital.…”

Section: Resultssupporting

confidence: 90%

“…The 1 1 Σ u - state, which was predicted as the ground state of Ni 2 at the ACPF level of theory ( Cheskidov et al, 2012 ) and found to lie quite close to a 1 Σ g + ground state in a limited CI study ( Ahmed and Nixon, 1979 ), was found at the GVVPT2 level to lie 91.09 cm −1 above the X 1 Γ g state at equilibrium. The 2 1 Σ u - state, however, lay much higher energetically (18,575.76 cm −1 above the ground state at equilibrium).…”

Section: Resultsmentioning

confidence: 90%

“…Experimental data on Ni 2 is sparse and the true ground state of the molecule is not unequivocally accepted. From the analysis of electronic absorption bands of Ni 2 in the visible spectral region in argon matrices, De Vore et al (De Vore et al, 1975) determined ω e 192 cm −1 , whereas a frequency of 380.9 cm −1 was found in solid argon matrix (Ahmed and Nixon, 1979). The latter result was later criticized by Rasanen et al (Rasanen et al, 1987) In photoelectron spectroscopic studies of Ni 2 -, ω e 280 ± 20 cm −1 was determined for the lowest electronic state of Ni 2 (Ho et al, 1993).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Low-Lying Electronic States of the Nickel Dimer

Tamukong

Hoffmann

2021

Front. Chem.

View full text Add to dashboard Cite

The generalized Van Vleck second order multireference perturbation theory (GVVPT2) method was used to investigate the low-lying electronic states of Ni2. Because the nickel atom has an excitation energy of only 0.025 eV to its first excited state (the least in the first row of transition elements), Ni2 has a particularly large number of low-lying states. Full potential energy curves (PECs) of more than a dozen low-lying electronic states of Ni2, resulting from the atomic combinations 3F4 + 3F4 and 3D3 + 3D3, were computed. In agreement with previous theoretical studies, we found the lowest lying states of Ni2 to correlate with the 3D3 + 3D3 dissociation limit, and the holes in the d-subshells were in the subspace of delta orbitals (i.e., the so-dubbed δδ-states). In particular, the ground state was determined as X 1Γg and had spectroscopic constants: bond length (Re) = 2.26 Å, harmonic frequency (ωe) = 276.0 cm−1, and binding energy (De) = 1.75 eV; whereas the 1 1Σg+ excited state (with spectroscopic constants: Re = 2.26 Å, ωe = 276.8 cm−1, and De = 1.75) of the 3D3 + 3D3 dissociation channel lay at only 16.4 cm−1 (0.002 eV) above the ground state at the equilibrium geometry. Inclusion of scalar relativistic effects through the spin-free exact two component (sf-X2C) method reduced the bond lengths of both of these two states to 2.20 Å, and increased their binding energies to 1.95 eV and harmonic frequencies to 296.0 cm−1 for X 1Γg and 297.0 cm−1 for 1 1Σg+. These values are in good agreement with experimental values of Re = 2.1545 ± 0.0004 Å, ωe = 280 ± 20 cm−1, and D0 = 2.042 ± 0.002 eV for the ground state. All states considered within the 3F4 + 3F4 dissociation channel proved to be energetically high-lying and van der Waals-like in nature. In contrast to most previous theoretical studies of Ni2, full PECs of all considered electronic states of the molecule were produced.

show abstract

Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Low-Lying Electronic States of the Nickel Dimer

Tamukong

Hoffmann

2021

Front. Chem.

View full text Add to dashboard Cite

show abstract

“…[66][67][68][69][70][71][72][73][74] The experimental bond distance for the Ni 2 molecule is 2.1545± 0.0004 Å. The nickel dimer is one of the most experimentally studied nickel clusters.…”

Section: Nimentioning

confidence: 99%

Assessment of density functional theory optimized basis sets for gradient corrected functionals to transition metal systems: The case of small Nin (n⩽5) clusters

Arvizu¹,

Calaminici²

2007

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…The electronically excited states are difficult to assign, but appear at wavelengths o450 nm. 34 The UV-vis spectra of Ni 2 shows several absorption bands at B3 eV. 35,36 The ds gpp u ( 3 p u or C state) is strongly bound, but overlaps with the dissociative ss gss u ( 3 S u À or B state).…”

Section: Resultsmentioning

confidence: 99%