H<sub>3</sub>P⋯AgI: generation by laser-ablation and characterization by rotational spectroscopy and ab initio calculations

Stephens, Susanna L.; Tew, David P.; Walker, Nicholas R.; Legon, A. C.

doi:10.1039/c6cp03512d

Cited by 13 publications

(8 citation statements)

References 55 publications

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“…[3][4][5][6][7][8][9][10]. The most powerful technique for conformational identification in the gas phase is rotational spectroscopy, which has been successfully applied in combination with laser ablation 11,12 to determine the conformations of many natural amino acids. [13][14][15][16] In the condensed phases, methods such as NMR and X-ray crystallography are also widely used.…”

Section: Introductionmentioning

confidence: 99%

Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

Comitani

Rossi

Ceriotti

et al. 2017

The Journal of Chemical Physics

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Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution The conformational free energy landscape of aspartic acid, a proteogenic amino acid involved in a wide variety of biological functions, was investigated as an example of the complexity that multiple rotatable bonds produce even in relatively simple molecules. To efficiently explore such a landscape, this molecule was studied in the neutral and zwitterionic forms, in the gas phase and in water solution, by means of molecular dynamics and the enhanced sampling method metadynamics with classical force-fields. Multi-dimensional free energy landscapes were reduced to bi-dimensional maps through the non-linear dimensionality reduction algorithm sketch-map to identify the energetically stable conformers and their interconnection paths. Quantum chemical calculations were then performed on the minimum free energy structures. Our procedure returned the low energy conformations observed experimentally in the gas phase with rotational spectroscopy [M. E. Sanz et al., Phys. Chem. Chem. Phys. 12, 3573 (2010)]. Moreover, it provided information on higher energy conformers not accessible to experiments and on the conformers in water. The comparison between different force-fields and quantum chemical data highlighted the importance of the underlying potential energy surface to accurately capture energy rankings. The combination of force-field based metadynamics, sketchmap analysis, and quantum chemical calculations was able to produce an exhaustive conformational exploration in a range of significant free energies that complements the experimental data. Similar protocols can be applied to larger peptides with complex conformational landscapes and would greatly benefit from the next generation of accurate force-fields.

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Section: Introductionmentioning

confidence: 99%

Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

Comitani

Rossi

Ceriotti

et al. 2017

The Journal of Chemical Physics

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“…Microwave spectroscopy has recently been applied to explore the molecular structures of complexes in which a Lewis base is attached to either CuX, AgX, or AuX (where X is a halogen atom) to form L· · · MX, [1][2][3][4][5][6][7][8][9][10][11] where, for example, L = H 2 O, 1,10 H 2 S, 3-5 NH 3 , 12 C 2 H 2 , 6,8,11 or CO. 13,14 The same technique has also been applied to study complexes that are similar in composition and structure but distinct in that L is not a typical Lewis base. For example, H 2 · · · MX, 15,16 Ar· · · MX, [17][18][19] Kr· · · MX, 18,20 and Xe· · · MX 21 have each been characterised.…”

Section: Introductionmentioning

confidence: 99%

Molecular geometries and other properties of H2O⋯AgI and H3N⋯AgI as characterised by rotational spectroscopy and ab initio calculations

Gougoula

Bittner

Mullaney

et al. 2017

The Journal of Chemical Physics

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The rotational spectra of HN⋯AgI and HO⋯AgI have been recorded between 6.5 and 18.5 GHz by chirped-pulse Fourier-transform microwave spectroscopy. The complexes were generated through laser vaporisation of a solid target of silver or silver iodide in the presence of an argon gas pulse containing a low concentration of the Lewis base. The gaseous sample subsequently undergoes supersonic expansion which results in cooling of rotational and vibrational motions such that weakly bound complexes can form within the expanding gas jet. Spectroscopic parameters have been determined for eight isotopologues of HN⋯AgI and six isotopologues of HO⋯AgI. Rotational constants, B; centrifugal distortion constants, D, D or Δ, Δ; and the nuclear quadrupole coupling constants, χ(I) and χ(I) - χ(I) are reported. HN⋯AgI is shown to adopt a geometry that has C symmetry. The geometry of HO⋯AgI is C at equilibrium but with a low barrier to inversion such that the vibrational wavefunction for the v = 0 state has C symmetry. Trends in the nuclear quadrupole coupling constant of the iodine nucleus, χ(I), of L⋯AgI complexes are examined, where L is varied across the series (L = Ar, HN, HO, HS, HP, or CO). The results of experiments are reported alongside those of ab initio calculations at the CCSD(T)(F12*)/AVXZ level (X = T, Q).

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“…The attachment of argon [27] leads to only a small change in the ionicity of the Ag− I bond on the formation of Ar…AgI. Carbon monoxide [3] and phosphine [28] each interact more strongly with the Ag− I sub-unit and cause a much greater change. The attachment of ethyne leads to a change that is intermediate between the extremes described above and comparable in magnitude to that caused by attachment [2] of NH 3 .…”

Section: Nuclear Quadrupole Coupling Constants and Ionic Charactermentioning

confidence: 99%

“…a Difference between the experimentally-determined (r 0 ) parameter and the (r e ) result calculated ab initio at the CCSD(T)(F12*)/AVTZ level. b. Refs [2], [23], [27], [28] and [32]. c. Numbers in parentheses are one standard deviation in units of the last significant figure (as given in the original source).…”

Section: Tablementioning

confidence: 99%

The microwave spectrum of the C2H2…AgI complex assigned and analysed using PGOPHER

Stephens

Tew²,

Walker³

et al. 2022

Journal of Molecular Spectroscopy

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H₃P⋯AgI: generation by laser-ablation and characterization by rotational spectroscopy and ab initio calculations

Abstract: The new compound H3P···AgI has been synthesized in the gas phase by means of the reaction of laser-ablated silver metal with a pulse of gas consisting of a dilute mixture of ICF3 and PH3 in argon.

Cited by 13 publications

References 55 publications

Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

Molecular geometries and other properties of H2O⋯AgI and H3N⋯AgI as characterised by rotational spectroscopy and ab initio calculations

The microwave spectrum of the C2H2…AgI complex assigned and analysed using PGOPHER

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H3P⋯AgI: generation by laser-ablation and characterization by rotational spectroscopy and ab initio calculations

Abstract: The new compound H3P···AgI has been synthesized in the gas phase by means of the reaction of laser-ablated silver metal with a pulse of gas consisting of a dilute mixture of ICF3 and PH3 in argon.

Cited by 13 publications

References 55 publications

Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

Molecular geometries and other properties of H2O⋯AgI and H3N⋯AgI as characterised by rotational spectroscopy and ab initio calculations

The microwave spectrum of the C2H2…AgI complex assigned and analysed using PGOPHER

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H₃P⋯AgI: generation by laser-ablation and characterization by rotational spectroscopy and ab initio calculations