Reactions between small organic molecules and Ag+ in the gas-phase. A theoretical study

Boutreau, Laurence; Léon, Emmanuelle; Luna, A.; Toulhoat, Pierre; Tortajada, Jeanine

doi:10.1016/s0009-2614(01)00189-0

Cited by 23 publications

(28 citation statements)

References 24 publications

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“…Although several experimental investigations of this complex have been performed, they have not been devoted to the elucidation of the exact structure of this system, but were limited to the evaluation of the binding energy 36–38. However, many calculations have been performed, using various levels of ab initio chemistry approaches:37, 39–48 in most cases a C 2 v structure was hypothesized. Only in refs.…”

Section: Resultsmentioning

confidence: 99%

Revisiting the geometry of nd¹⁰ (n+1)s⁰ [M(H₂O)]^p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (M^p+ = Cu⁺, Zn²⁺, Ag⁺, Cd²⁺, Au⁺, Hg²⁺)

Gourlaouen¹,

Piquemal²,

Saue³

et al. 2005

J Comput Chem

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Hartree-Fock and DFT (B3LYP) nonrelativistic (scalar relativistic pseudopotentials for the metallic cation) and relativistic (molecular four-component approach coupled to an all-electron basis set) calculations are performed on a series of six nd10 (n+1)s0 [M(H2O)]p+ complexes to investigate their geometry, either planar C2v or nonplanar C(s). These complexes are, formally, entities originating from the complexation of a water molecule to a metallic cation: in the present study, no internal reorganization has been found, which ensures that the complexes can be regarded as a water molecule interacting with a metallic cation. For [Au(H2O)]+ and [Hg(H2O)]2+, it is observed that both electronic correlation and relativistic effects are required to recover the C(s) structures predicted by the four-component relativistic all-electron DFT calculations. However, including the zero-point energy corrections makes these shallow C(s) minima vanish and the systems become floppy. In all other systems, namely [Cu(H2O)]+, [Zn(H2O)]2+, [Ag(H2O)]+, and [Cd(H2O)]2+, all calculations predict a C2v geometry arising from especially flat potential energy surfaces related to the out-of-plane wagging vibration mode. In all cases, our computations point to the quasi-perfect transferability of the atomic pseudopotentials considered toward the molecular species investigated. A rationalization of the shape of the wagging potential energy surfaces (i.e., single well vs. double well) is proposed based on the Constrained Space Orbital Variation decompositions of the complexation energies. Any way of stabilizing the lowest unoccupied orbital of the metallic cation is expected to favor charge-transfer (from the highest occupied orbital(s) of the water ligand), covalence, and, consequently, C(s) structures. The CSOV complexation energy decompositions unambiguously reveal that such stabilizations are achieved by means of relativistic effects for [Au(H2O)]+, and, to a lesser extent, for [Hg(H2O)]2+. Such analyses allow to numerically quantify the rule of thumb known for Au+ which, once again, appears as a better archetype of a relativistic cation than Hg2+. This observation is reinforced due to the especially high contribution of the nonadditive correlation/relativity terms to the total complexation energy of [Au(H2O)]+.

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Section: Resultsmentioning

confidence: 99%

Revisiting the geometry of nd¹⁰ (n+1)s⁰ [M(H₂O)]^p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (M^p+ = Cu⁺, Zn²⁺, Ag⁺, Cd²⁺, Au⁺, Hg²⁺)

Gourlaouen¹,

Piquemal²,

Saue³

et al. 2005

J Comput Chem

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“…Previous ab initio studies have characterized nucleic acids and metal cations, [28][29][30][31][32][33][34][35][36][37] or alkali metals. 35,[38][39][40] However, structural data on metal DNA mispairs is scarce. 4 Only few structures have been suggested for the Ag c-a mispair, e.g.…”

Section: Introductionmentioning

confidence: 99%

Structure and bonding of Ag(I)–DNA base complexes and Ag(I)–adenine–cytosine mispairs: An ab Initio study

Schreiber

González

2007

J Comput Chem

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High level ab initio calculations have been carried out to characterize the structure, bonding and energetics of Ag(I)-DNA base complexes, including adenine or cytosine, as well as Ag(I)-adenine-cytosine mispairs. The interactions of the Ag cation in all binding sites of all adenine and cytosine tautomers have been considered. The calculations show that in gas phase the canonical form of cytosine is stabilized upon metalation, whereas the lowest energy structure of Ag-adenine correspond to a rare tautomer. Interestingly, the theoretical inspection of metalated adenine-cytosine mispair reveals that the most stable structures are formed from the canonical cytosine and adenine tautomers. The lowest energy structure is planar with adenine and cytosine hydrogen-bonded. Within few kcal/mol nonplanar, conformationally very flexible structures are found, in which the Ag(I) crosslinks an endocyclic nitrogen of adenine and the oxygen of cytosine. Metalated reverse-Wobble type of structures, on the contrary, are predicted much higher in energy.

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“…They were determined by high-pressure mass spectrometry (HPMS), 14 radiative dissociation kinetics in a Fourier transform-ion cyclotron resonance mass spectrometer (RA/FT-ICR), 16 supersonic molecular beam/charge transfer photodissociation, [19][20][21] and threshold-CID methods. 15,17,22,23 These experimental studies were often accompanied [16][17][18][19][20][21][22][23] or augmented [24][25][26][27] by molecular orbital calculations, which provide complimentary information on the binding geometries/modes and rationalization of experimental observations. An example is the determination of the relative Ag + affinities of the twenty naturally-occurring amino acids by the mass spectrometric kinetic method, 6 and rationalization of their relative order and possible binding modes/sites by density functional theory (DFT) calculations has been reported recently.…”

Section: Introductionmentioning

confidence: 99%

Silver(i) affinities of amides: a combined ab initio and experimental study

Ng¹,

Li²,

Wo³

et al. 2004

Phys. Chem. Chem. Phys.

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Reactions between small organic molecules and Ag+ in the gas-phase. A theoretical study

Cited by 23 publications

References 24 publications

Revisiting the geometry of nd¹⁰ (n+1)s⁰ [M(H₂O)]^p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (M^p+ = Cu⁺, Zn²⁺, Ag⁺, Cd²⁺, Au⁺, Hg²⁺)

Revisiting the geometry of nd¹⁰ (n+1)s⁰ [M(H₂O)]^p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (M^p+ = Cu⁺, Zn²⁺, Ag⁺, Cd²⁺, Au⁺, Hg²⁺)

Structure and bonding of Ag(I)–DNA base complexes and Ag(I)–adenine–cytosine mispairs: An ab Initio study

Silver(i) affinities of amides: a combined ab initio and experimental study

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Reactions between small organic molecules and Ag+ in the gas-phase. A theoretical study

Cited by 23 publications

References 24 publications

Revisiting the geometry of nd10 (n+1)s0 [M(H2O)]p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (Mp+ = Cu+, Zn2+, Ag+, Cd2+, Au+, Hg2+)

Revisiting the geometry of nd10 (n+1)s0 [M(H2O)]p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (Mp+ = Cu+, Zn2+, Ag+, Cd2+, Au+, Hg2+)

Structure and bonding of Ag(I)–DNA base complexes and Ag(I)–adenine–cytosine mispairs: An ab Initio study

Silver(i) affinities of amides: a combined ab initio and experimental study

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Resources

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Revisiting the geometry of nd¹⁰ (n+1)s⁰ [M(H₂O)]^p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (M^p+ = Cu⁺, Zn²⁺, Ag⁺, Cd²⁺, Au⁺, Hg²⁺)

Revisiting the geometry of nd¹⁰ (n+1)s⁰ [M(H₂O)]^p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (M^p+ = Cu⁺, Zn²⁺, Ag⁺, Cd²⁺, Au⁺, Hg²⁺)