Geometries of H2S⋯MI (M = Cu, Ag, Au) complexes studied by rotational spectroscopy: The effect of the metal atom

Bittner, Dror M.; Tew, David P.; Walker, Nicholas R.; Legon, A. C.

doi:10.1063/1.4967477

Cited by 12 publications

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“…The method employed to generate H 3 N· · · AgI is identical to that used previously during a study of H 2 S· · · AgI. 3,5 A gas sample containing a low concentration of precursors is diluted in argon and prepared at a total pressure of 6 bars. The sample is prepared to contain ∼1.5% CF 3 I and ∼4.0% NH 3 .…”

Section: A Experimentalmentioning

confidence: 99%

“…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%

“…H 2 O· · · MX complexes were observed to undergo rapid inversion between two equivalent C s geometries on the time scale of a molecular rotation such that the geometry of H 2 O· · · MX is effectively C 2v (planar) in the v = 0 state. 1,[3][4][5]10,22 Rotational a) Authors to whom correspondence should be addressed: Nick.Walker@ newcastle.ac.uk and a.c.legon@bristol.ac.uk spectroscopy has proven to be a powerful tool for investigation of the structure and dynamics in such complexes. Previous studies have made comparisons with hydrogenand halogen-bonded complexes of similar geometrical structure.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: A Experimentalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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“…Systematic studies of microwave spectra of complexes of hydrogen halides with aliphatic amines show the important role of interaction of an electron shell of an halide atom with the electric quadrupole moment of a nucleus—nuclear quadrupolar constant (NQC, χ ) . NQC could be used to characterize redistribution of electron density in local intermolecular interactions.…”

Section: Resultsmentioning

confidence: 99%

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

2019

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The change of cooperativity of FH···Cl− hydrogen bonds upon sequential addition of up to six FH molecules to the Cl− first coordination sphere is investigated. The geometry of clusters [(FH) nCl]− (n = 1…6) was calculated (CCSD/aug‐cc‐pVDZ) and compared with [(FH) nF]− clusters. The geometry is determined by the symmetry‐driven electrostatic requirements and also by the fact that formation of each new FH···Cl− bond creates a depression in the chlorine's electron cloud on the opposite side of Cl− (σ‐hole), which limits the range of directions available for subsequent H‐bond formation. The mutual influence of FH···Cl− hydrogen bonds is anticooperative—the addition of each FH molecule weakens H‐bonds by 23–16% and decreases their covalent character (as seen by LMO‐EDA decomposition and QTAIM analysis). Anticooperativity effects could be tracked by spectroscopic parameters (frequency of local HF mode νFH, chemical shift δH, spin–spin coupling constants 1JFH, 1hJHCl, 2hJFCl and nuclear quadrupolar constants χ18F, χD, and χ35Cl. © 2019 Wiley Periodicals, Inc.

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“…Thef irst hint of ap ossibility that K a = 1l ines could be observed for (H 2 S) 2 came during rotational spectroscopic studies of H 2 S···MI (M = Cu, Ag,A u) complexes [41] by Medcraft et al using ab roadband microwave spectrometer at Newcastle University. [42,43] They noted 6l ines,w hich were suspected to be due to transitions of the deuterated isotopomers of (H 2 S) 2 ,s ee below.T his motivated us to reexamine the rotational spectrum of (H 2 S) 2 .A fter as hort period of time,weobserved and assigned several K a = 1lines for the parent and other deuterated isotopomers of (H 2 S) 2 .…”

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The H₂S Dimer is Hydrogen‐Bonded: Direct Confirmation from Microwave Spectroscopy

et al. 2018

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The K a = 1t ransitions of the H 2 Sd imer and several isotopomers were observed in apulsed nozzle Fourier transform microwave spectrometer.T hese provide unambiguous evidence that the H 2 Sd imer has an anisotropic structure exhibiting an S À H···S hydrogen bond. Theh ydrogen bond distance (H···S) is determined to be 2.778(9) ,w hich is smaller than the sum of van der Waals radii of Ha nd S( ca. 3 ). Thehydrogen bond angle ]S-H···S is determined to be 175(7)8 8.T he structure is similar to that of the well-explored H 2 Od imer, though in bulk, ice,a nd solid H 2 Sa ppear very different. Thes tructure determined from microwave spectroscopy is in very good agreement with the result from highlevel theoretical calculations.Thewater dimer,(H 2 O) 2 ,isprobably the most extensively studied hydrogen-bonded system, both experimentally [1][2][3][4][5][6][7] and theoretically. [8][9][10][11][12][13][14][15] Hydrogen bonding [16,17] is crucial to all life on earth. It is significantly weaker than ac ovalent bond but strong enough to establish the highly ordered structure of water ice.Itplays acrucial role in the structure of DNAand in passing the genetic code.The dissociation energy of the water dimer, D 0 ,l eading to two isolated water molecules,w as measured experimentally to be 1105 AE 10 cm À1 (13.2 AE 0.12 kJ mol À1 ). [18] There have been an umber of reports on the dimer of its sulfur analogue,( H 2 S) 2 . [19][20][21][22][23][24][25][26] Lemke has recently reported CCSD(T) calculations with complete basis set extrapolation on H 2 Sdimer and the dissociation energy is about 7kJmol À1 . [23] Them icrowave spectrum of the H 2 S dimer is interesting to examine because of clear structural differences between the condensed phases of H 2 Oand H 2 S. In the most commonly encountered form of solid water,ice,H 2 O is surrounded by four other water molecules.A ni ndividual molecule of H 2 Si ss urrounded by twelve H 2 Sm olecules in isomorphs of solid H 2 S [27,28] (as shown in Figure 1). Only asphere could accommodate 12 different neighbors,implying that each H 2 Smolecule interacts with neighboring molecules through an effectively spherical [29] potential energy surface. Thed ramatic difference between the condensed phases of water and hydrogen sulfide led Pauling [27] to conclude that the structure of water ice is mediated by anisotropic hydrogen bonds whereas the structure of solid H 2 Si sd etermined by isotropic van der Waals interactions.Optimized geometries of (H 2 O) 2 and (H 2 S) 2 calculated ab initio are similar, and both are hydrogen-bonded. Experimental studies on the H 2 Sdimer are fewer in number than those on the H 2 Od imer. Matrix isolation studies were not conclusive with respect to the structure of the H 2 Sd imer in solid N 2 , [30] O 2 , [31] Kr, [32] Xe, [33] and Ar [34] because H 2 Sreadily aggregates at low temperature to form higher oligomers,and infrared shifts are much smaller than those observed for H 2 Ocomplexes.Anexperiment that explored the gas phase structure of (H 2 S) 2 by infrared spectro...

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Geometries of H2S⋯MI (M = Cu, Ag, Au) complexes studied by rotational spectroscopy: The effect of the metal atom

Cited by 12 publications

References 63 publications

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

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

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

The H₂S Dimer is Hydrogen‐Bonded: Direct Confirmation from Microwave Spectroscopy

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Geometries of H2S⋯MI (M = Cu, Ag, Au) complexes studied by rotational spectroscopy: The effect of the metal atom

Cited by 12 publications

References 63 publications

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

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

Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6)

The H2S Dimer is Hydrogen‐Bonded: Direct Confirmation from Microwave Spectroscopy

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Resources

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Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

The H₂S Dimer is Hydrogen‐Bonded: Direct Confirmation from Microwave Spectroscopy