Geometries and Energy Separations of Electronic States of GeF2, SnF2, and PbF2 and Their Positive Ions

Dai, Dingguo; Al‐Zahrani, Mesfer M.; Balasubramanian, K.

doi:10.1021/j100088a024

Cited by 29 publications

(40 citation statements)

References 4 publications

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“…Especially methylene [2][3][4] and its halogen derivatives [5][6][7][8][9][10][11][12][13] have received much interest recently by computations, whereas relatively fewer studies appeared on the heavier analogues (i.e., substituting carbon by other members of its group). [14][15][16][17][18] Focusing mainly on relativistic effects, Balasubramanian and co-workers performed systematic studies on AX 2 molecules, A ) Ge, Sn, Pb, X ) H, F, Cl, Br, I, during the 1990s. [14][15][16][17] They carried out multireference configuration interaction calculations including single and double excitations (MRSDCI), with the complete active space self-consistent field (CASSCF) wave function as the reference function.…”

Section: Introductionmentioning

confidence: 99%

Molecular Structure of Carbene Analogues: A Computational Study

Szabados

Hargittai

2003

J. Phys. Chem. A

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Systematic computational studies on the dihydrides and dihalides of group 14 elements have been performed, for their ground state and first excited state. We present equilibrium geometries of the lowest lying singlet and triplet states and singlet-triplet energy separation data on the whole series obtained by the CCSD(T) method. Scalar relativistic effects are taken into account by applying effective core potentials (ECP) from the fourth period on. The performance of two sets of core potentials is compared and set against previous theoretical results and available experimental information. Expected trends and anomalies in the variation of geometrical parameters are discussed.

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Section: Introductionmentioning

confidence: 99%

Molecular Structure of Carbene Analogues: A Computational Study

Szabados

Hargittai

2003

J. Phys. Chem. A

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“…Theoretical data on CO/Rh species, coming from different levels of computation, have also been reported, [6][7][8][9][10][11][12][13][14] mainly concerning the geometrical and electronic structures as well as vibrational frequencies of RhCO and Rh(CO) 2 . The geometrical and vibrational features of Rh(CO) 3 and Rh(CO) 4 computed by using hybrid and nonlocal functionals within density functional theory (DFT) are also available.…”

Section: Introductionmentioning

confidence: 99%

CO Interaction with Small Rhodium Clusters from Density Functional Theory: Spectroscopic Properties and Bonding Analysis

2001

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Density functional computations have been performed to determine equilibrium geometrical structures, magnetic properties, and vibrational frequencies of a series of Rh x (CO) y (x e 4, y e 2) clusters. The results are compared with experiments on CO adsorption on small rhodium aggregates deposited onto a thin, well-ordered alumina film. The CO stretching frequency as a function of rhodium cluster topology and spin-state is reported and discussed. The considered rhodium monocarbonyls are found to exhibit nonzero magnetic moments. They show a more pronounced dependence of the CO-stretching frequency on the magnetic properties than on the number of rhodium atoms. The CO bonding behavior in the formation of Rh x (CO) y species is rationalized on the basis of the molecular orbital and the natural bond order analysis.

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“…singlets 1 A 1 with largely destabilized triplet states 3 B 1 . The calculated Δ E s‐t steadily increases descending group 14 . Likewise, in a series of halogen‐substituted heavy carbenes (X 2 M:) for a given halogen, Δ E s‐t increases from Si to Pb, whereas for a given group 14 element, Δ E s‐t decreases from F to I .…”

Section: Introductionmentioning

confidence: 99%

“…The calculated Δ E s‐t steadily increases descending group 14 . Likewise, in a series of halogen‐substituted heavy carbenes (X 2 M:) for a given halogen, Δ E s‐t increases from Si to Pb, whereas for a given group 14 element, Δ E s‐t decreases from F to I . Stabilization of carbenes to the extent of allowing their generation as persistent species (triplet carbenes) or even isolation as stable derivatives (singlet carbenes) is to be noted.…”

Section: Introductionmentioning

confidence: 99%

Cyclonona‐3,5,7‐trienylidene and its Si, Ge, Sn, and Pb analogs versus their α‐halogenated derivatives at B3LYP and MP2 methods

Koohi

2019

J of Physical Organic Chem

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Five sets of group 14 sextet cyclic unsaturated divalent species including carbenes (1X), silylenes (2X), germylenes (3X), stannylenes (4X), and plumbylenes (5X) are compared and contrasted at B3LYP/AUG‐cc‐pVTZ//B3LYP/6‐311 + G* and MP2/AUG‐cc‐pVTZ//MP2/6‐311 + G* levels of theory, where X = H, F, Cl, and Br. The scrutinized carbenes consisting of cyclonona‐3,5,7‐trienylidene (1H) and its 2,2,9,9‐tetrahalo derivatives (1Cl, 1Br) appear as boat shaped minima except for 1H which turns out as a boat shaped transition state for having a negative force constant. All of carbenes (1H, 1Cl, and 1Br) have triplet ground states except for 1F. In contrast, all of the corresponding 2X‐ 5X metallylenes appear as singlet boat shaped minima on their potential energy surfaces. Stability (estimated by ΔEs‐t, ie, energy gap between singlet [s] and triplet states) appear as a function of size and decreases by going down in group 14 column: 5X > 4X > 3X > 2X > 1X. Exclusive of carbene set, within other four sets stability decreases by going down in group 17 column: Br > Cl > F > H. Hence, singlet 2,2,9,9‐tetrabromocyclonona‐3,5,7‐trienplumbylene, 5Br, appears as the most stable sextet divalent with no tendency for dimerization. Comparison is extended to the structural parameters, band gap, nucleophilicity, electrophilicity, isodesmic reactions, and dimerization.

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Geometries and Energy Separations of Electronic States of GeF2, SnF2, and PbF2 and Their Positive Ions

Cited by 29 publications

References 4 publications

Molecular Structure of Carbene Analogues: A Computational Study

Molecular Structure of Carbene Analogues: A Computational Study

CO Interaction with Small Rhodium Clusters from Density Functional Theory: Spectroscopic Properties and Bonding Analysis

Cyclonona‐3,5,7‐trienylidene and its Si, Ge, Sn, and Pb analogs versus their α‐halogenated derivatives at B3LYP and MP2 methods

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